Laminated films and laminated members

Abstract

To provide a laminate film capable of being molded in a complicated shape.SOLUTION: A laminate film which comprises a transparent support base material, an uncured hard coat layer formed on at least one surface of the transparent support base material, and an uncured optical interference layer formed on the uncured hard coat layer is such that: the uncured hard coat layer includes an active energy ray-curable hard coat layer-forming composition; the uncured optical interference layer includes an active energy ray-curable optical interference layer-forming composition; a thickness of the transparent support base material is 50 μm or more and 600 μm or less; a view luminous reflectance including regular reflection light and measured from a side of the uncured optical interference layer is 0.1% or more and 4.0% or less; and an elongation percentage at 160°C is 50% or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a laminated film and a laminated member. [Background technology]

[0002] Displays are used in a variety of fields, including computers, televisions, mobile phones, and portable information terminal devices (tablet PCs, mobile devices, electronic organizers, etc.), as well as in digital meters, instrument panels, navigation systems, console panels, center clusters, heater control panels, and other in-vehicle display panels. Such products are often covered with a protective material. The protective material is usually obtained by forming a film having a hard coat layer.

[0003] In some cases, a low refractive index layer is further provided on the display protective material for the purpose of reducing the reflectance of the viewing side surface.

[0004] JP2015-004937A (Patent Document 1) teaches a laminated film in which a hard coat layer and a low refractive index layer (light interference layer) are laminated in this order on a transparent support. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2015-004937 A Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, displays have been molded into various shapes depending on the purpose, such as use and design. Therefore, protective materials for displays are also required to be moldable into complex shapes. However, it is difficult to mold the laminated film described in Patent Document 1 into complex shapes.

[0007] The present invention is intended to solve the above-mentioned problems in the conventional art, and an object of the present invention is to provide a laminated film that can be formed into a complex shape. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention provides the following aspects. [1] A transparent support substrate; an uncured hard coat layer formed on at least one surface of the transparent support substrate; an uncured light interference layer formed on the uncured hard coat layer, The uncured hard coat layer contains an active energy ray-curable hard coat layer-forming composition, the uncured light interference layer contains an active energy ray-curable light interference layer-forming composition, The thickness of the transparent support substrate is 50 μm or more and 600 μm or less, a luminous reflectance including specular reflection light measured from the uncured light interference layer side is 0.1% or more and 4.0% or less; A laminated film having a stretch ratio of 50% or more at 160°C. [2] The laminate film according to the above-mentioned [1], wherein the uncured optical interference layer has a thickness of 15 nm or more and 200 nm or less. [3] The laminate film according to the above [1] or [2], wherein the uncured hard coat layer has a thickness of 2 μm or more and 30 μm or less. [4] The laminate film according to any one of the above [1] to [3], wherein the hardness measured from the uncured light interference layer side by a nanoindentation method is 0.1 GPa or more and 0.5 GPa or less. [5] Accumulated light intensity: 500mJ / cm 2 The laminate film according to any one of the above [1] to [4], wherein the hardness of the laminate film irradiated with active energy rays, as measured by a nanoindentation method from the optical interference layer side, is more than 0.5 GPa and not more than 1.2 GPa. [6] The integrated light dose on the laminated film is 500 mJ / cm 2 5. The laminate film according to any one of the above [1] to [5], wherein when the surface of the light interference layer is rubbed 5,000 times while applying a vertical load of 4.9 N after irradiation with an active energy ray, no scratches are visible on the light interference layer. [7] The laminate film according to any one of the above [1] to [6], further comprising at least one uncured functional layer between the uncured hard coat layer and the uncured light interference layer. [8] A laminated member comprising a cured laminated film according to any one of the above [1] to [7]. Effect of the Invention

[0009] The laminated film of the present invention can be formed into a complex shape. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] As a protective film for a display, a laminated film called a pre-cured type may be used. The hard coat layer and the optical interference layer contained in the pre-cured laminated film are usually cured in a step prior to the pre-forming step, that is, in the step of forming each layer, as shown in Patent Document 1. Therefore, during the pre-forming, the laminated film cannot follow the mold having a complex shape, and cracks may occur in the laminated film.

[0011] One way to make a pre-cured laminate film conform to a mold is to lower the crosslink density of the laminate film, but if the crosslink density is low, it is difficult to obtain sufficient mechanical properties.

[0012] From this viewpoint, it has been conceived that the hard coat layer and the light interference layer are not cured in the manufacturing process of the laminate film. A laminate film having an uncured hard coat layer and an uncured light interference layer is an after-cure type.

[0013] Since the after-cure type laminate film is subjected to the preforming process in an uncured state, it can be molded into a complex shape without cracking. Since the occurrence of cracks is suppressed, the appearance of the molded product is good, and the functions of the hard coat layer and the light interference layer are effectively exerted. In addition, since the stretching ratio at 160°C is 50% or more, and the thickness of the transparent support substrate is 50 μm or more and 600 μm or less, the obtained laminate member has sufficient rigidity even when molded into a complex shape.

[0014] Furthermore, since there is no need to stretch the film after curing, each layer can be formed from a layer-forming composition that has a high crosslink density, which means that each layer can have a higher hardness after curing.

[0015] In addition, since both the hard coat layer and the optical interference layer are uncured, the adhesion between the layers is high. Furthermore, by performing heat treatment, the unevenness of the surface of each layer can be leveled. This allows a laminated film with high smoothness to be obtained.

[0016] The luminous reflectance of the laminated film, including the regular reflection light, is 0.1% or more and 4.0% or less. Therefore, it has excellent anti-reflection performance. The laminated member obtained by curing this also has excellent anti-reflection performance. The anti-reflection effect reduces the reflection of external light on the laminated member.

[0017] A. Laminated film The laminated film according to the present embodiment has a transparent supporting substrate, an uncured hard coat layer formed on at least one surface of the transparent supporting substrate, and an uncured light interference layer formed on the uncured hard coat layer. The uncured hard coat layer contains an active energy ray-curable hard coat layer-forming composition. The uncured light interference layer contains an active energy ray-curable light interference layer-forming composition.

[0018] The term "uncured" refers to a state in which the film is not completely cured. The hard coat layer and the optical interference layer included in the laminate film may be in a semi-cured state. The laminate film is of an after-cure type.

[0019] Hardening is synonymous with "hardened and dried" as defined in JIS K 5500 (paint terminology). That is, hardening refers to the state in which a) the coating surface is dry and hard, when the center of a test piece is pinched firmly between the thumb and index finger, no indentation is left on the coating surface due to fingerprints, no movement of the coating film is felt, and when the coating surface is rubbed rapidly and repeatedly with the fingertips, no scratches are left.

[0020] Accumulated light intensity: 100mJ / cm 2 It can be said that the laminated film irradiated with the active energy rays is cured.

[0021] Similarly, semi-curing is synonymous with "semi-cured dry" as defined in JIS K 5500 (paint terminology). In other words, semi-curing refers to the state when the painted surface is dry to the touch when the center of the painted surface is rubbed lightly with a fingertip without leaving any marks. 2 More than 100mJ / cm 2 A laminated film irradiated with active energy rays of less than 1000 nm can be said to be semi-cured.

[0022] The term "uncured" refers to the fact that the hard coat layer and the optical interference layer have not been exposed to active energy rays or have been exposed to less than 1 mJ / cm 2 This refers to a state in which the body is exposed to actinic radiation of less than 1000 nm.

[0023] (Luminous reflectance) The luminous reflectance including regular reflection light measured from the uncured light interference layer side of the laminate film is 0.1% or more and 4.0% or less. In other words, the lower limit of the luminous reflectance of the laminate film is 0.1% and the upper limit is 4.0%. That is, the laminate film has excellent antireflection properties. The laminate member obtained by curing the laminate film also has excellent antireflection properties. Therefore, the laminate member has little reflection due to external light, and has good display characteristics and good visibility. The luminous reflectance of the laminate member can also be 0.1% or more and 4.0% or less.

[0024] The luminous reflectance being within this range also indicates that the occurrence of interphase between the uncured hard coat layer and the uncured light interference layer is suppressed, and a clear interface is formed between the two layers.

[0025] The luminous reflectance of the laminated film is preferably from 0.1% to 3.0%, and more preferably from 0.1% to 2.5%.

[0026] The luminous reflectance is obtained by measuring all reflected light, including specular reflected light. In other words, the luminous reflectance is measured by the so-called SCI (Specular Component Include) method. This method is not easily affected by the surface condition of the object to be measured, so it is possible to measure the luminous reflectance of an uncured layer.

[0027] Specifically, the luminous reflectance of the laminated film can be measured by the following method. A black paint (e.g., product name: CZ-805 BLACK (manufactured by Nikko Bix Co., Ltd.) is applied to the surface of the transparent support substrate opposite the uncured hard coat layer using a bar coater so that the dry film thickness is 3 μm to 6 μm. After that, it is left to dry for 5 hours in a room temperature environment to prepare evaluation sample M.

[0028] The luminous reflectance by the SCI method in the wavelength range of 380 nm to 780 nm is measured from the light interference layer side of the obtained evaluation sample M using a spectrophotometer (e.g. SD7000 manufactured by Nippon Denshoku Industries Co., Ltd.) The luminous reflectance of the laminated film according to this embodiment is 0.1% to 4.0% in the wavelength range of 380 nm to 780 nm.

[0029] The luminous reflectance of the laminated member can be measured as follows. The evaluation sample M created above was irradiated with an integrated light dose of 500 mJ / cm 2The laminated film is irradiated with active energy rays to prepare an evaluation sample N. The luminous reflectance is measured from the light interference layer side of the obtained evaluation sample N in the same manner as above. Before the irradiation with active energy rays, the laminated film may be heat-treated at 80° C. for 1 hour.

[0030] (Stretching rate) The stretch ratio of the laminated film at 160°C is 50% or more. In this case, the laminated film is sufficiently stretched at a molding temperature of 150°C or more and 190°C or less. Therefore, the laminated film can be shaped into a complex three-dimensional shape without cracking. In particular, damage to the laminated film is easily suppressed in the preforming process. Therefore, a laminated member having the functions of a hard coat layer and a light interference layer and a complex three-dimensional shape can be obtained. After the preforming process, the laminated film is molded, for example, by insert molding, etc., according to the required physical properties, shape, etc.

[0031] The functions of the hard coat layer and the light interference layer are, for example, excellent hard coat performance and anti-reflection performance. The hard coat performance includes, for example, high hardness, abrasion resistance, and chemical resistance.

[0032] The stretch ratio of the laminated film at 160°C is preferably 60% or more, more preferably 70% or more. The stretch ratio of the laminated film at 160°C may be less than 400%, may be less than 350%, or may be less than 300%. In particular, when the laminated film is stretched at a stretch ratio of about 250%, it is desirable that no breakage, cracks, changes in appearance, etc. are visually observed. The stretch ratio of the laminated member obtained by curing the laminated film at 160°C may be less than 15% and 5% or less.

[0033] The stretch ratio can be measured, for example, as follows. Prepare a tensile tester with a chuck distance of 150 mm and an evaluation sample cut to a length of 200 mm and a width of 10 mm. Stretch the long side of the evaluation sample by 50% under conditions of a tensile force of 5.0 kgf and a tensile speed of 300 mm / min in a 160°C atmosphere. Observe the stretched evaluation sample using a microscope with a magnification of 1000 times or more to check for the presence or absence of cracks exceeding 100 μm in length and 1 μm in width.

[0034] If no cracks are found, a new sample is cut out and the long side is stretched to 60%. The same procedure is then used to check for the presence or absence of cracks. This procedure is repeated while increasing the stretch ratio by 10%, and the stretch ratio at which a crack of the above size is first found is regarded as the stretch ratio of the laminated film. The initial stretch may be set to 250% and the test may be performed in the same manner as above.

[0035] (Thickness) The thickness of the transparent supporting substrate is 50 μm or more and 600 μm or less. This allows the laminated film to maintain its rigidity even when stretched. In addition, warping of the laminated film and the laminated member is easily suppressed. Furthermore, the transparent supporting substrate and the laminated film can be wound into a roll, so that roll-to-roll processing can be performed. The thickness of the transparent supporting substrate is preferably 100 μm or more, more preferably 200 μm or more. The thickness of the transparent supporting substrate is preferably 500 μm or less, more preferably 480 μm or less, even more preferably 450 μm or less, and particularly preferably 400 μm or less.

[0036] The thickness of the uncured light interference layer is not particularly limited, and may be appropriately set according to the design wavelength. The thickness of the uncured light interference layer is, for example, 15 nm or more and 200 nm or less. The thickness of the uncured light interference layer is preferably 60 nm or more, more preferably 65 nm or more. The thickness of the uncured light interference layer is preferably 180 nm or less. When the thickness of the uncured light interference layer is in this range, good anti-reflection properties can be imparted to the laminated member.

[0037] The thickness of the uncured hard coat layer is not particularly limited. For example, the hard coat layer forming composition is applied so that the thickness of the uncured hard coat layer is 2 μm or more and 30 μm or less. The uncured hard coat layer is a hard coat layer that has been dried and is not cured (hereinafter, simply referred to as an uncured hard coat layer). When the uncured hard coat layer has such a thickness, warping after curing is easily suppressed. In addition, a hard coat layer having excellent hard coat performance is obtained.

[0038] The thickness of the uncured hard coat layer is more preferably 3 μm or more, and particularly preferably 25 μm or less, and particularly preferably 20 μm or less.

[0039] (hardness) The hardness of the laminated film is not particularly limited. In terms of being easily prevented from being damaged in the post-process, the hardness Hb of the laminated film measured from the optical interference layer side by the nanoindentation method is preferably 0.1 GPa or more. If the hardness Hb is 0.1 GPa or more, defects such as squeegee marks or suction marks are prevented, and the yield is easily improved.

[0040] The hardness Hb is preferably 0.5 GPa or less, since the adhesion between the uncured hard coat layer and the uncured light interference layer is easily improved. The hardness Hb of the laminated film can be regarded as the maximum hardness of the uncured hard coat layer or the uncured light interference layer. When the hardness Hb is 0.5 GPa or less, when the uncured light interference layer is laminated on the uncured hard coat layer, the two are easily adhered to each other. Furthermore, when the uncured hard coat layer and the uncured light interference layer are laminated by bonding, air is prevented from entering between the layers (air entrapment). Specifically, the hardness Hb is preferably 0.1 GPa or more and 0.5 GPa or less.

[0041] The hardness Hb is more preferably 0.15 GPa or more, further preferably 0.2 GPa or more, and particularly preferably 0.25 GPa or more. The hardness Hb is more preferably 0.45 GPa or less, further preferably 0.42 GPa or less, and particularly preferably 0.4 GPa or less.

[0042] The hardness Hb of the laminated film is calculated based on the value measured by the nanoindentation method from the light interference layer side of the laminated film. In the nanoindentation method, it is preferable to measure within a range of 300 nm from the surface of the light interference layer, particularly within a range of 50 nm to 100 nm from the surface layer of the light interference layer. The hardness Hb of the laminated film is, for example, the maximum hardness calculated from the value measured by the nanoindentation method within a range of 50 nm to 100 nm from the surface layer of the light interference layer.

[0043] The hardness of the laminated member is usually higher than that of the laminated film, and therefore the hardness Ha measured by the nanoindentation method from the optical interference layer side of the laminated member can be set based on the hardness Hb of the laminated film.

[0044] When the hardness Hb of the laminated film is 0.5GPa, the cumulative light dose is 500mJ / cm 2 The hardness Ha of the laminated film (laminate member) irradiated with the active energy rays is measured by a nanoindentation method from the light interference layer side, and is, for example, more than 0.5 GPa and not more than 1.2 GPa. The hardness Ha of the laminated member may be more than 0.7 GPa and not more than 1.2 GPa.

[0045] When the hardness Hb of the laminated film is 0.4 GPa, the hardness Ha of the laminated member is, for example, more than 0.4 GPa and not more than 1.2 GPa. The hardness Ha of the laminated member may be more than 0.7 GPa and not more than 1.2 GPa. When the hardness Ha is more than 0.5 GPa, the hard coat performance of the laminated member is easily improved.

[0046] The hardness by the nanoindentation method is determined, for example, by the continuous stiffness measurement method using a nanoindentation device. In the continuous stiffness measurement method, a quasi-static test load (direct current (DC) load) and a minute load (alternating current (AC) load) are applied to the sample. This causes the force acting on the sample to vibrate minutely. The stiffness with respect to depth is calculated from the vibration component of the resulting displacement and the phase difference between the displacement and the load. This allows a continuous profile of hardness with respect to depth to be obtained.

[0047] For example, the Advanced Dynamic E and H.NMT method can be used for the continuous stiffness measurement method. As the nanoindentation device, the iMicro Nanoindenter manufactured by NANOMECHANICS, INC. can be used. In this case, the load and stiffness can be calculated using iMicro's dedicated software. A load is applied to the sample by the indenter until the maximum load of 50 mN is reached. As the indenter, for example, a Verkovich type diamond indenter is used. When performing the measurement and calculating the stiffness, the Poisson's ratio of the coating layer, the load, etc. can be set to appropriate values.

[0048] (Wear resistance) It is desirable for the laminated member to have excellent abrasion resistance. For example, when an active energy ray is irradiated to a laminated film with an integrated light amount of 500 mJ / cm 2 The laminated member is obtained by irradiating the light. The surface of the optical interference layer is then rubbed 5000 times with a normal load of 4.9 N. It is preferable that no scratches are visible on the laminated member after this abrasion test. No scratches are visible means that a decrease in visibility due to a change in appearance is suppressed.

[0049] The abrasion test is carried out under the above conditions using a known method. A frictional device with a cotton cloth attached is usually used for the abrasion test. A normal load of 4.9 N is applied to the sample by the frictional device.

[0050] Before being irradiated with active energy rays, the laminated film may be heat-treated for 30 to 60 seconds in an atmosphere at 150 to 190° C. This makes the surface of the laminated film flat by leveling, making it easier to further improve the abrasion resistance.

[0051] "No visible scratches" means that scratches cannot be observed by visual inspection. "Scratches" refer to, for example, surface roughness. As long as scratches are not observed by visual inspection, very slight scratches may be observed when observing the sample after the abrasion test using a microscope with a magnification of 100 times.

[0052] The transparent supporting substrate and each layer of the laminate film of this embodiment will be described in further detail below.

[0053] [Transparent support base material] The transparent support substrate is not particularly limited as long as it is transparent. This enhances the design when a decorative layer described later is provided on the laminate member. Specifically, being transparent means that the total light transmittance is 80% or more. The total light transmittance of the transparent support substrate is 80% or more, and preferably 90% or more. The total light transmittance can be measured by a method conforming to JIS K 7361-1. As the transparent support substrate, those known in the art can be used without any particular limitation. The transparent support substrate may be colorless or colored.

[0054] The transparent support substrate is appropriately selected depending on the application. Examples of the transparent support substrate include polyester films such as polycarbonate (PC) films, polyethylene terephthalate, and polyethylene naphthalate; cellulose films such as diacetyl cellulose and triacetyl cellulose; acrylic films such as polymethyl methacrylate (PMMA); styrene films such as polystyrene and acrylonitrile-styrene copolymers; olefin films such as polyvinyl chloride, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; and amide films such as nylon and aromatic polyamide. The transparent support substrate may be a film containing a resin such as polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinyl butyral, polyarylate, polyoxymethylene, or an epoxy resin, or a film containing a mixture of these polymers.

[0055] The transparent supporting substrate may be a laminate of a plurality of films, for example, a laminate of a film made of an acrylic resin and a film made of a polycarbonate resin.

[0056] The transparent support substrate may be optically anisotropic or isotropic. The magnitude of birefringence of the optically anisotropic transparent support substrate is not particularly limited. The retardation of the anisotropic transparent support substrate may be 1 / 4 (λ / 4) of the wavelength or 1 / 2 (λ / 2) of the wavelength.

[0057] [Uncured hard coat layer] The uncured hard coat layer contains an active energy ray-curable hard coat layer-forming composition (hereinafter, sometimes referred to as composition HC). The composition HC is cured by active energy rays.

[0058] The active energy rays are ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, γ rays, etc. It is particularly preferable that the composition HC is of an ultraviolet ray curing type.

[0059] The composition HC includes an active energy ray curable resin component. The active energy ray curable resin component has a polymerizable group (polymerizable unsaturated group, typically a (meth)acryloyl group) having an unreacted unsaturated bond. The unreacted polymerizable unsaturated group has, for example, a double bond represented by C=C. When exposed to active energy rays, the unreacted polymerizable unsaturated group reacts and the double bond disappears. The disappearance of the double bond can be confirmed by a known method, for example, FT-IR, etc.

[0060] Accumulated light dose of 500mJ / cm on uncured hard coat layer 2 When the uncured hard coat layer is irradiated with active energy rays, 10% to 100% of the unreacted polymerizable unsaturated groups contained in the uncured hard coat layer disappear.

[0061] Accumulated light dose of 500mJ / cm on uncured hard coat layer 2 The percentage of unreacted polymerizable unsaturated groups lost when irradiated with active energy rays may be 15% or more and 90% or less, may be 20% or more and 80% or less, may be 30% or more and 70% or less, or may be 30% or more and 60% or less.

[0062] Accumulated light dose of 30mJ / cm on uncured hard coat layer 2 The disappearance rate of the unreacted polymerizable unsaturated groups when irradiated with the active energy rays may be 10% or more and 50% or less.

[0063] Accumulated light dose of 5mJ / cm on uncured hard coat layer 2 The disappearance rate of the unreacted polymerizable unsaturated groups upon irradiation with the active energy rays may be 10% or more and 30% or less, or may be 10% or more and 50% or less.

[0064] The greater the disappearance rate of unreacted polymerizable groups, the higher the crosslink density. Therefore, the hardness of the hard coat layer is high and the stretch ratio is likely to be low. By adjusting the integrated light amount of the active energy rays, the hardness and / or stretch ratio of the hard coat layer can be controlled.

[0065] For example, a laminated film that has not been irradiated with active energy rays is preformed. Then, before the main molding process, the laminated film is irradiated with active energy rays to an extent that the laminated film does not completely harden, and the stretch ratio of the laminated film is set to 1% to 15%. This allows the laminated film to be slightly stretched to an extent that the shape applied in the preforming process can be maintained. Therefore, even if there is a slight dimensional difference between the mold used in the preforming process and the mold used in the main molding process, the laminated film can be shaped in the main molding process while suppressing the occurrence of cracks. In addition, the hardness of the hard coat layer is increased by the irradiation of active energy rays, so that the hard coat layer is prevented from sticking to the mold in the main molding process. Examples of the main molding include injection molding such as insert molding.

[0066] Specifically, after the preforming process, the laminated film is exposed to an integrated light dose of 1 mJ / cm 2 More than 100mJ / cm 2 The laminated film is irradiated with the following active energy rays (semi-curing). This makes it easier for the laminated film to be shaped along the mold used in the actual molding while suppressing the occurrence of cracks. After that, the actual molding is performed. Next, the cumulative light dose is 100 mJ / cm2. 2 The above active energy rays are irradiated (main curing).

[0067] The disappearance rate of unreacted polymerizable unsaturated groups does not change much before and after heating. In other words, the curing of the composition HC hardly progresses due to the heat treatment. Therefore, before the semi-curing or full curing, the uncured hard coat layer can be subjected to heat treatment without affecting the adhesion of the hard coat layer or the stretch ratio of the laminated film. The heat treatment can increase the smoothness of the hard coat layer. Therefore, the smoothness of the obtained laminated member is also improved.

[0068] The molecular weight distribution of the active energy ray-curable resin component also does not change much before and after heat treatment. The fact that the molecular weight distribution does not change much means that the weight average molecular weight peak, and if there are multiple molecular weight peaks, the height shift of each molecular weight peak and the lateral shift are all within the range of ±5%.

[0069] The heat treatment is carried out under conditions that do not affect the performance of the hard coat layer. The heat treatment conditions may be appropriately set according to the composition of the composition HC. The heat treatment temperature may be 90°C or more and 200°C or less, 100°C or more and 200°C or less, or 110°C or more and 200°C or less. The heat treatment time may be 10 seconds or more and 10 minutes or less.

[0070] The heat treatment may be performed by utilizing the heat applied in the preforming step. By performing the preforming at a temperature of about 150° C. or higher and 190° C. or lower, the uncured hard coat layer can be sufficiently leveled during the preforming.

[0071] (Composition HC) The hard coat layer is laminated with the uncured light interference layer in an uncured state. Furthermore, the laminated film is subjected to various processes in an uncured state. Therefore, the uncured hard coat layer is required to have high hardness, low tack and to be less susceptible to contamination, to be prevented from being damaged or changing in appearance during processing, and to be prevented from curling due to differences in heat shrinkage from other layers.

[0072] Damage during processing includes, for example, dents such as suction marks and squeegee marks in the printing process, and changes in appearance during processing include, for example, foaming and cracks in the preforming process.

[0073] These requirements can be met by controlling the hardness, rigidity, smoothness, tackiness, etc. of the uncured hard coat layer. The above physical properties of the uncured hard coat layer can be adjusted by the thickness thereof and the composition of the composition HC, etc.

[0074] <Resin component> The composition HC contains an active energy ray-curable resin component. The active energy ray-curable resin component contains a monomer, oligomer, or polymer that is crosslinked and cured by active energy rays.

[0075] Specific examples of active energy ray curable resin components include monomers, oligomers, or polymers (hereinafter, sometimes referred to as reactive resins) having at least one polymerizable unsaturated group. More specific examples of active energy ray curable resin components include (meth)acrylate compounds such as (meth)acrylate monomers, (meth)acrylate oligomers, and (meth)acrylate polymers, each of which has at least one unsaturated double bond; urethane (meth)acrylate compounds such as urethane (meth)acrylate monomers, urethane (meth)acrylate oligomers, and urethane (meth)acrylate polymers; and silicon (meth)acrylate compounds such as silicon (meth)acrylate monomers, silicon (meth)acrylate oligomers, and silicon (meth)acrylate polymers. These may be used alone or in combination of two or more. "(Meth)acrylate" refers to acrylate and / or methacrylate.

[0076] Among these, reactive resins are preferred because the crosslink density of the cured hard coat layer is likely to be high by the reactive resin, and therefore excellent hard coat performance is exhibited.

[0077] The weight average molecular weight (Mw) of the reactive resin is preferably 5000 to 100000, more preferably 6000 to 95000, and even more preferably 9000 to 90000. The glass transition temperature (Tg) of the reactive resin is, for example, preferably 40°C to 120°C, and more preferably 40°C to 110°C. This makes it easier to further improve the smoothness and rigidity of the uncured hard coat layer. In particular, reactive acrylic resins are preferred.

[0078] The weight average molecular weight (Mw) can be calculated from a chromatogram measured by gel permeation chromatography, based on the molecular weight of standard polystyrene.

[0079] Composition HC may include a non-reactive resin. Composition HC may include a non-reactive resin together with a reactive resin. Composition HC may include two or more reactive resins and two or more non-reactive resins.

[0080] A non-reactive resin is a resin that does not react or shows little reactivity even when irradiated with active energy rays (typically ultraviolet rays). Examples of non-reactive resins include urethane resins, acrylic resins, polyester resins, and epoxy resins. The weight average molecular weight (Mw) of the non-reactive resin is preferably 5000 to 100000, more preferably 6000 to 95000.

[0081] When multiple reactive resins and / or non-reactive resins are included, the Mw of one resin may be 5000 or more and 100000 or less. The Mw of the other resin is not particularly limited. The Mw of the other resin may be, for example, 10000 or more and 80000 or less. By using resins having various weight average molecular weights in combination, the uncured hard coat layer is likely to have high smoothness, and the hardness of the uncured hard coat layer is easily adjusted to a desired range.

[0082] Composition HC preferably contains at least one of a non-reactive acrylic resin and a reactive acrylic resin, which, without being limited to any particular theory, can increase the smoothness and stiffness of the uncured hard coat layer.

[0083] The total content of the reactive acrylic resin and / or the non-reactive acrylic resin is preferably more than 20 parts by mass and not more than 60 parts by mass, more preferably 30 parts by mass or more and not more than 60 parts by mass, and particularly preferably 35 parts by mass or more and not more than 60 parts by mass, relative to 100 parts by mass of the solid content of the composition HC.

[0084] The solid content of the composition HC is the above-mentioned active energy ray-curable resin component, non-reactive resin, photopolymerization initiator, inorganic oxide fine particles, etc. The solid content of the optical interference layer-forming composition is the same.

[0085] The composition HC preferably contains at least one selected from a polyfunctional (meth)acrylate compound, a polyfunctional urethane (meth)acrylate compound, and a polyfunctional silicon (meth)acrylate compound. As a result, the uncured hard coat layer exhibits high viscosity at room temperature, while the viscosity is reduced by heating. Therefore, the uncured hard coat layer exhibits good adhesion to the uncured light interference layer, and is easily shaped into a complex shape. Furthermore, the cured hard coat layer has a high crosslink density, so the hard coat performance is further improved.

[0086] In particular, the composition HC preferably contains a reactive acrylic resin and / or a non-reactive acrylic resin and a multifunctional urethane (meth)acrylate monomer and / or oligomer. This makes it easier to further improve the shaping property of the uncured hard coat layer and the adhesion to the uncured light interference layer. In addition, the hard coat performance of the cured hard coat layer is also easier to improve.

[0087] In particular, the composition HC preferably contains a reactive acrylic resin and / or a non-reactive acrylic resin having an Mw of 5000 to 100000, and a polyfunctional urethane (meth)acrylate monomer and / or oligomer having an acrylate equivalent of 100 g / eq. to 200 g / eq. This further improves the low tackiness of the uncured hard coat layer.

[0088] The content of the polyfunctional urethane (meth)acrylate monomer and / or oligomer is preferably 5 parts by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 70 parts by mass or less, and particularly preferably 13 parts by mass or more and 68 parts by mass or less, relative to 100 parts by mass of the solid content of the composition HC.

[0089] The acrylate equivalent of the polyfunctional urethane (meth)acrylate monomer and / or oligomer may be 110 g / eq. or more and 180 g / eq. or less, or 115 g / eq. or more and 160 g / eq. or less.

[0090] The composition HC may contain a reactive acrylic resin and / or a non-reactive acrylic resin, and at least one member selected from the group consisting of polyfunctional silicon (meth)acrylate monomers and / or oligomers, and inorganic oxide fine particles.

[0091] In particular, the composition HC preferably contains a reactive acrylic resin and / or a non-reactive acrylic resin, a polyfunctional silicon (meth)acrylate monomer and / or oligomer, and inorganic oxide fine particles.

[0092] Although it should not be interpreted as being limited to a particular theory, the polyfunctional silicon (meth)acrylate monomer and / or oligomer can reduce the surface tension of the uncured hard coat layer and improve the leveling property. The inorganic oxide fine particles suppress the volumetric shrinkage of the uncured hard coat layer and tend to increase the rigidity. Therefore, the appearance change during the manufacturing process of the uncured hard coat layer is easily suppressed. Furthermore, the appearance change and curling of the cured hard coat layer are also suppressed. In addition, the tackiness of the cured hard coat layer is reduced and the abrasion resistance is easily increased.

[0093] The Mw of the polyfunctional silicon (meth)acrylate monomer and / or oligomer is preferably 700 or more and 100,000 or less, more preferably 800 or more and 90,000 or less, and more preferably 800 or more and 85,000 or less.

[0094] The content of the polyfunctional silicon (meth)acrylate monomer and / or oligomer is preferably 0.1 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 45 parts by mass or less, and particularly preferably 1.5 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of the solid content of the composition HC.

[0095] The content of the inorganic oxide fine particles is preferably 1 to 55 parts by mass, more preferably 10 to 50 parts by mass, and particularly preferably 12 to 40 parts by mass, per 100 parts by mass of the solid content of the composition HC.

[0096] The inorganic oxide fine particles are not particularly limited. Examples of inorganic oxide fine particles include silica (SiO2) particles, alumina particles, titania particles, tin oxide particles, antimony-doped tin oxide (ATO) particles, zinc oxide particles, and zirconia oxide particles. The surface of the inorganic oxide fine particles may be modified with a functional group containing an unsaturated double bond. As the functional group, a (meth)acryloyl group is preferable. Among them, from the viewpoint of cost and paint stability, silica particles and alumina particles are preferable, and silica particles and alumina particles whose surfaces are modified with a functional group are particularly preferable. The form of the inorganic oxide fine particles may be a sol.

[0097] The primary particle diameter of the inorganic oxide fine particles is not particularly limited. From the viewpoint of transparency and paint stability, the primary particle diameter of the inorganic oxide fine particles is preferably 5 nm or more and 100 nm or less. The primary particle diameter of the inorganic oxide fine particles is a value measured using image processing software from a cross-sectional image obtained by an electron microscope. The average particle diameter of other granular materials can also be determined by the same method.

[0098] (Silica particles) Examples of commercially available silica particles (colloidal silica) are given below. Manufactured by Nissan Chemical Industries: IPA-ST, MEK-S TM, IBK-S T, PGMST, XBA-S T, MEK-AC-2101, MEK-AC-2202, MEKAC-4101M IB K-SD Manufactured by Fuso Chemical Industry Co., Ltd.: PL-1-IPA, PL-1-TOL, PL-2-IPA, PL-2-MEK, PL-3-TOL JGC Catalysts and Chemicals: OSCAL series, ELECOM series BYK Japan: NANOBYK-3605

[0099] (Alumina particles) Examples of commercially available alumina particles are given below. Sumitomo Osaka Cement: AS-150I, AS-150T BYK Japan: NANOBYK-3601, NANOBYK-3602, NANOBYK-3610

[0100] (zirconia oxide particles) Examples of commercially available zirconia oxide particles are given below. Sakai Chemical Industry Co., Ltd.: SZR-K, SZR-KM CIK Nanotech: ZRANB15WT%-P02, ZRMIBK15WT%-P01, ZRMIBK15WT%-F85 Solar: NANON5ZR-010, NANON5ZR-020

[0101] Examples of the (meth)acrylate monomer or oligomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, acrylic acid, methacrylic acid, isostearyl (meth)acrylate, ethoxylated o-phenylphenol acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol acrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, N-methylol (meth)acrylamide, and N-hydroxy(meth)acrylamide.

[0102] (Polyfunctional (meth)acrylate monomer or oligomer) Examples of commercially available polyfunctional (meth)acrylate monomers or oligomers are given below. DPHA (manufactured by Daicel Allnex), PETRA (manufactured by Daicel Allnex: pentaerythritol triacrylate), PETIA (manufactured by Daicel Allnex), Aronix M-403 (manufactured by Toagosei: dipentaerythritol penta- and hexaacrylate), Aronix M-402 (manufactured by Toagosei: dipentaerythritol penta- and hexaacrylate), Aronix M-400 (manufactured by Toagosei: dipentaerythritol penta- and hexaacrylate), SR-399 (manufactured by Arkema: dipentaerythritol hydroxypentaacrylate), KAYARAD DPHA (manufactured by Nippon Kayaku), KAYARAD DPHA-2C (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-404, M-405, M-406, M-450, M-305, M-309, M-310, M-315, M-320, TO-1200, TO-1231, TO-595, TO-756 (all manufactured by Toagosei Co., Ltd.), KAYARD D-310, D-330, DPHA, DPHA-2C (all manufactured by Nippon Kayaku Co., Ltd.), Nikalac MX-302 (manufactured by Sanwa Chemical Co., Ltd.)

[0103] The (meth)acrylate polymer may be, for example, a polymer of at least one of the above-mentioned (meth)acrylate monomers and oligomers.

[0104] (Polyfunctional urethane (meth)acrylate monomer or oligomer) Examples of commercially available polyfunctional urethane (meth)acrylate monomers or oligomers are shown below. Bifunctional urethane (meth)acrylates ("UX-2201", "UX-8101", "UX-6101" manufactured by Nippon Kayaku Co., Ltd., "UF-8001" and "UF-8003" manufactured by Kyoeisha Chemical Co., Ltd., "Ebecryl244", "Ebecryl284", "Ebecryl2002", "Ebecryl4835", "Ebecryl4883", "Ebecryl8807", "Ebecryl6700" manufactured by Daicel-Allnex Co., Ltd.), trifunctional urethane (meth)acrylates ("Ebecryl254", "Ebecryl264", "Ebecryl265" manufactured by Daicel-Allnex Co., Ltd.), tetrafunctional urethane (meth)acrylates ("Ebecryl8210" manufactured by Daicel-Allnex Co., Ltd.), hexafunctional urethane (meth)acrylates (Daicel "Ebecryl1290k", "Ebecryl5129", "Ebecryl220", "KRM-8200", "Ebecryl1290N" manufactured by Daicel Allnex Co., Ltd.), 9-functional urethane (meth)acrylate ("KRM-7804" manufactured by Daicel Allnex Co., Ltd.), 10-functional urethane (meth)acrylate ("KRM-8452", "KRM-8509" manufactured by Daicel Allnex Co., Ltd.), 15-functional urethane (meth)acrylate ("KRM-8655" manufactured by Daicel Allnex Co., Ltd.)

[0105] The urethane (meth)acrylate monomer or oligomer can also be prepared, for example, by reacting a polycarbonate diol, a (meth)acrylate compound containing a hydroxyl group and an unsaturated double bond group in the molecule, and a polyisocyanate.

[0106] The urethane (meth)acrylate polymer may be, for example, a polymer of at least one of the above-mentioned urethane (meth)acrylate monomers and oligomers.

[0107] The silicon (meth)acrylate monomer or oligomer is a (meth)acrylate monomer or oligomer having a siloxane bond. A functional group containing a fluorine atom may be bonded to the silicon atom.

[0108] (Polyfunctional silicon (meth)acrylate monomer or oligomer) Examples of commercially available polyfunctional silicon (meth)acrylate monomers or oligomers are given below. Compounds containing methacryloyl and acryloyl groups BYK: BYK-UV3500, BYK-UV3570 Shin-Etsu Chemical Co., Ltd.: Shin-Etsu Silicone X-22-164, Shin-Etsu Silicone X-22-164AS, Shin-Etsu Silicone X-22-164A, Shin-Etsu Silicone X-22-164B, Shin-Etsu Silicone X-22-164C, Shin-Etsu Silicone X-22-164E, Shin-Etsu Silicone X-22-174DX, Shin-Etsu Silicone X-22-2426, Shin-Etsu Silicone X-22-2475, KER-4000-UV, KER-4700-UV, KER-4710-UV, KER-4800-UV JNC: FM-0711, FM-0721, FM-0725, TM-0701, FM-7711, FM-7721, FM-7725 Evonik Japan: TEGO(R) Rad 2010, TEGO(R) Rad 2011

[0109] Polyfunctional silicon (meth)acrylate monomers or oligomers containing fluorine atoms Mitsubishi Chemical: Shiko UV-AF305 T&K TOKA: ZX-212, ZX-214-A Shin-Etsu Chemical Co., Ltd.: KY-1203

[0110] The composition HC may contain a reactive acrylic resin and / or a non-reactive acrylic resin, and at least one selected from the group consisting of a polyfunctional urethane acrylate monomer and / or oligomer, a fluorine atom-containing polyfunctional silicon (meth)acrylate monomer and / or oligomer, and inorganic oxide fine particles.

[0111] <Photopolymerization initiator> The composition HC preferably contains a photopolymerization initiator, which facilitates the polymerization of the active energy ray-curable resin component.

[0112] Examples of the photopolymerization initiator include an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a titanocene-based photopolymerization initiator, and an oxime ester-based polymerization initiator.

[0113] Examples of alkylphenone-based photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

[0114] Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0115] An example of the titanocene photopolymerization initiator is bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.

[0116] Examples of oxime ester polymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, and 2-(2-hydroxyethoxy)ethyl ester. These photopolymerization initiators may be used alone or in combination of two or more.

[0117] Among these, at least one selected from the group consisting of 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2,2-dimethoxy-1,2-diphenylethan-1-one is preferred.

[0118] The content of the photopolymerization initiator is preferably from 0.01 to 10 parts by mass, and more preferably from 1 to 10 parts by mass, relative to 100 parts by mass of the solid content of the composition HC.

[0119] <Solvent> The composition HC may contain a solvent. The solvent is not particularly limited and is appropriately selected in consideration of the components contained in the composition, the type of transparent support substrate, the coating method, and the like.

[0120] Examples of the solvent include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and isobutyl alcohol; and halogen solvents such as dichloromethane and chloroform. These solvents are used alone or in combination of two or more. Among them, ester solvents, ether solvents, alcohol solvents, and ketone solvents are preferred.

[0121] <others> Composition HC may contain various additives as necessary, such as antistatic agents, plasticizers, surfactants, antioxidants, UV absorbers, surface conditioners, leveling agents, and light stabilizers (e.g., hindered amine light stabilizers (HALS)).

[0122] [Uncured optical interference layer] The uncured light interference layer contains an active energy ray-curable light interference layer-forming composition (hereinafter, sometimes referred to as composition R). Composition R is cured by active energy rays. Composition R is preferably cured by the same type of active energy rays as composition HC.

[0123] The optical interference layer can function as a layer having a low refractive index. The refractive index of the cured optical interference layer is, for example, 1.35 or more and 1.55 or less, can be 1.38 or more and 1.55 or less, or can be 1.38 or more and 1.51 or less. This allows it to exhibit good anti-reflection properties.

[0124] The optical interference layer may function as a layer having a high refractive index or a layer having a medium refractive index. The refractive index of the high refractive index layer may be more than 1.55 and 2.00 or less. The refractive index of the medium refractive index layer is not particularly limited, and may be between the low refractive index layer and the high refractive index layer. The refractive index of the medium refractive index layer may be, for example, 1.55 or more and 1.70 or less.

[0125] The thickness of the optical interference layer is not particularly limited. The thickness of the optical interference layer may be 10 nm or more and 300 nm or less. The thickness of the optical interference layer is preferably 15 nm or more, more preferably 40 nm or more, and particularly preferably 60 nm or more. The thickness of the optical interference layer is preferably 200 nm or less, more preferably 180 nm or less, and particularly preferably 150 nm or less.

[0126] The composition R contains an active energy ray-curable resin component. The active energy ray-curable resin component has a polymerizable group (polymerizable unsaturated group, typically a (meth)acryloyl group) having an unreacted unsaturated bond.

[0127] Accumulated light dose of 500mJ / cm on uncured light interference layer 2 When the uncured light interference layer is irradiated with active energy rays, 10% to 100% of the unreacted polymerizable unsaturated groups contained in the uncured light interference layer disappear.

[0128] Accumulated light dose of 500mJ / cm on uncured light interference layer 2 The percentage of unreacted polymerizable unsaturated groups lost when irradiated with active energy rays may be 15% or more and 90% or less, may be 20% or more and 80% or less, may be 30% or more and 70% or less, or may be 30% or more and 60% or less.

[0129] Accumulated light dose of 5 mJ / cm on uncured light interference layer 2The disappearance rate of the unreacted polymerizable unsaturated groups upon irradiation with the active energy rays may be 10% or more and 30% or less, or may be 10% or more and 50% or less.

[0130] Accumulated light dose of 30 mJ / cm on uncured light interference layer 2 The disappearance rate of the unreacted polymerizable unsaturated groups when irradiated with the active energy rays may be 10% or more and 50% or less.

[0131] The greater the disappearance rate of unreacted polymerizable groups, the higher the crosslink density. Therefore, the hardness of the light interference layer is high and the stretching rate is likely to be low. By adjusting the integrated light amount of the active energy rays, the hardness and / or stretching rate of the light interference layer can be controlled.

[0132] Even in the uncured light interference layer, the disappearance rate of unreacted polymerizable unsaturated groups does not change much before and after the heat treatment. In other words, the curing of the composition R hardly progresses due to the heat treatment. Therefore, before the active energy ray irradiation step, the uncured light interference layer can be subjected to a heat treatment without affecting the adhesion of the light interference layer or the stretch ratio of the laminated film. The heat treatment can increase the smoothness of the light interference layer. Therefore, the smoothness of the obtained laminated member is also improved.

[0133] The heat treatment is carried out under conditions that do not affect the performance of the optical interference layer. The heat treatment conditions may be appropriately set according to the composition of the composition R. The heat treatment temperature may be 90°C or more and 200°C or less, 100°C or more and 200°C or less, or 110°C or more and 200°C or less. The heat treatment time may be 10 seconds or more and 10 minutes or less.

[0134] This heat treatment may also be performed by utilizing the heat applied in the preforming step, so that the uncured optical interference layer can be sufficiently leveled during the preforming step.

[0135] (Composition R) The light interference layer is laminated with the uncured hard coat layer in an uncured state. Furthermore, as described above, the laminated film is subjected to various processes in an uncured state. Therefore, the light interference layer is required to have the same performance as the hard coat layer in addition to anti-reflection performance. In particular, the light interference layer is required to have excellent anti-reflection performance, low tack and difficult to be contaminated, and to suppress damage and appearance change during processing. An example of the appearance change during processing is a streak called a zipping mark that occurs when a protective film is peeled off.

[0136] These requirements can be met by controlling the hardness, rigidity, smoothness, tackiness, etc. of the uncured light interference layer. The above physical properties of the uncured light interference layer can be adjusted by the thickness thereof and the composition of Composition R, etc.

[0137] <Resin component> The composition R contains an active energy ray curable resin component. The active energy ray curable resin component contains a monomer, oligomer, or polymer (reactive resin) that is crosslinked and cured by active energy rays. Examples of the active energy ray curable resin component contained in the composition R include the same as the active energy ray curable resin component contained in the composition HC.

[0138] Among them, reactive resins are preferred. The weight average molecular weight (Mw) of the reactive resin is preferably 5000 to 100000, more preferably 6000 to 95000, and even more preferably 9000 to 90000. The glass transition temperature (Tg) of the reactive resin is, for example, preferably 40°C to 120°C, and more preferably 40°C to 110°C. This makes it easier to further improve the smoothness and rigidity of the uncured optical interference layer. In particular, reactive acrylic resins are preferred.

[0139] The composition R may contain a non-reactive resin. Examples of the non-reactive resin include the same non-reactive resin contained in the composition HC. The weight average molecular weight (Mw) of the non-reactive resin is preferably 5000 or more and 100000 or less, more preferably 6000 or more and 95000 or less.

[0140] Composition R may contain a non-reactive resin together with a reactive resin. Composition R may contain two or more reactive resins and two or more non-reactive resins.

[0141] The total content of the reactive acrylic resin and / or the non-reactive acrylic resin is preferably more than 5 parts by mass and not more than 40 parts by mass, more preferably 10 parts by mass or more and 30 parts by mass or less, and particularly preferably 15 parts by mass or more and 25 parts by mass or less, relative to 100 parts by mass of the solid content of composition R.

[0142] When multiple types of reactive resins and / or non-reactive resins are included, the Mw of one type of resin may be 5000 or more and 100000 or less. The Mw of the other resins is not particularly limited. The Mw of the other resins may be, for example, 10000 or more and 80000 or less. By using resins having various weight average molecular weights in combination, the uncured light interference layer is likely to have high smoothness, and the hardness of the uncured light interference layer is easily adjusted to a desired range.

[0143] Among them, it is preferable that the composition R contains a reactive acrylic resin and / or a non-reactive acrylic resin, and a multifunctional urethane (meth)acrylate monomer and / or oligomer. This makes it easier to obtain an uncured light interference layer that has low tack and is less susceptible to contamination. Furthermore, the adhesion between the uncured hard coat layer and the uncured light interference layer is improved. Examples of the multifunctional urethane (meth)acrylate monomer and oligomer include the same multifunctional urethane (meth)acrylate monomer and oligomer contained in the above-mentioned composition HC.

[0144] In particular, composition R preferably contains a reactive acrylic resin and / or a non-reactive acrylic resin having an Mw of 5,000 or more and 100,000 or less, and a polyfunctional urethane (meth)acrylate monomer and / or oligomer having an acrylate equivalent of 100 g / eq. or more and 200 g / eq. or less.

[0145] The content of the polyfunctional urethane (meth)acrylate monomer and / or oligomer is preferably 5 parts by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 70 parts by mass or less, and particularly preferably 13 parts by mass or more and 68 parts by mass or less, relative to 100 parts by mass of the solid content of composition R.

[0146] The acrylate equivalent of the polyfunctional urethane (meth)acrylate monomer and / or oligomer may be 110 g / eq. or more and 180 g / eq. or less, or 115 g / eq. or more and 160 g / eq. or less.

[0147] Composition R may contain a reactive acrylic resin and / or a non-reactive acrylic resin, and at least one selected from the group consisting of a polyfunctional silicon (meth)acrylate monomer and / or oligomer, a fluororesin, and inorganic oxide fine particles.

[0148] In particular, composition R preferably contains a reactive acrylic resin and / or a non-reactive acrylic resin, a polyfunctional silicon (meth)acrylate monomer and / or oligomer, a fluororesin, and inorganic oxide fine particles.

[0149] Although not limited to a particular theory, the polyfunctional silicon (meth)acrylate monomer and / or oligomer can reduce the surface tension of the uncured light interference layer, improve the leveling property, and reduce tackiness. The fluororesin imparts slipperiness to the uncured and cured light interference layer, which makes it easier to improve the abrasion resistance. The inorganic oxide fine particles suppress the volumetric shrinkage of the uncured light interference layer and make it easier to increase the rigidity. Therefore, the appearance change during the manufacturing process of the uncured light interference layer is easily suppressed. Furthermore, the appearance change and curling of the cured light interference layer are also suppressed. In addition, the tackiness of the cured light interference layer is reduced and the abrasion resistance is easily increased.

[0150] Examples of the polyfunctional silicone (meth)acrylate monomer and / or oligomer include the same polyfunctional silicone (meth)acrylate monomer and / or oligomer contained in the above composition HC. Examples of inorganic oxide fine particles include the same inorganic oxide fine particles as those contained in the above composition HC.

[0151] The Mw of the polyfunctional silicon (meth)acrylate monomer and / or oligomer is preferably 700 or more and 100,000 or less, more preferably 800 or more and 90,000 or less, and more preferably 800 or more and 85,000 or less.

[0152] The content of the polyfunctional silicon (meth)acrylate monomer and / or oligomer is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 48 parts by mass or less, and particularly preferably 13 parts by mass or more and 48 parts by mass or less, per 100 parts by mass of the solid content of composition R.

[0153] The fluororesin does not contain a siloxane bond, and at least a part of the hydrogen of the alkyl chain is replaced with fluorine. Examples of the fluororesin include perfluorooctyl acrylate and acrylic modified perfluoropolyether. The fluororesin may have a (meth)acryloyl group partially replaced with fluorine.

[0154] Examples of commercially available fluororesins are given below. DIC: Megafac RS-72-K, Megafac RS-75, Megafac RS-76-E, Megafac RS-76-NS, Megafac RS-77 Daikin Industries: Optool DAC-HP Solvay Solexis: FLUOROLINK MD700, FLUOROLINK AD1700 Neos: Futergent 601ADH2

[0155] The content of the fluororesin is preferably from 0.1 to 10 parts by mass, more preferably from 1 to 8 parts by mass, and particularly preferably from 1.5 to 7 parts by mass, relative to 100 parts by mass of the solid content of composition R.

[0156] The content of the inorganic oxide fine particles is preferably 1 to 55 parts by mass, more preferably 10 to 50 parts by mass, and particularly preferably 12 to 40 parts by mass, per 100 parts by mass of the solid content of Composition R.

[0157] The composition R may contain at least one selected from a polyfunctional (meth)acrylate compound, a polyfunctional urethane (meth)acrylate compound, and a polyfunctional silicon (meth)acrylate compound. This allows the cured light interference layer to have a high crosslink density and therefore excellent hard coat performance. In addition, the transparency of the cured light interference layer is easily improved. As the polyfunctional (meth)acrylate compound, the polyfunctional urethane (meth)acrylate compound, and the polyfunctional silicon (meth)acrylate compound, for example, those exemplified for the above composition HC can be selected.

[0158] Composition R may contain at least one selected from the group consisting of reactive acrylic resins, non-reactive acrylic resins, polyfunctional urethane acrylate monomers and / or oligomers, fluorine atom-containing polyfunctional silicon (meth)acrylate monomers and / or oligomers, fluororesins, and inorganic oxide fine particles.

[0159] Composition R may contain a reactive acrylic resin and / or a non-reactive acrylic resin, and at least one selected from the group consisting of a polyfunctional urethane acrylate monomer and / or oligomer, a fluorine atom-containing polyfunctional silicon (meth)acrylate monomer and / or oligomer, a fluororesin, and inorganic oxide fine particles.

[0160] <Photopolymerization initiator> Composition R preferably contains a photopolymerization initiator. This facilitates polymerization of the active energy ray curable resin component. Examples of photopolymerization initiators include those exemplified for composition HC above.

[0161] Among these, at least one selected from the group consisting of 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2,2-dimethoxy-1,2-diphenylethan-1-one is preferred.

[0162] The content of the photopolymerization initiator is preferably 0.01 parts 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, relative to 100 parts by mass of the solid content of the composition R.

[0163] <Solvent> The composition R may contain a solvent. The solvent is not particularly limited, and is appropriately selected in consideration of the components contained in the composition, the type of transparent support substrate, the coating method, etc. As the solvent, those exemplified for the composition HC above can be selected. Among them, ester-based solvents, ether-based solvents, alcohol-based solvents, and ketone-based solvents are preferred.

[0164] <Refractive index reducing component> The composition R for forming the low refractive index layer preferably contains a refractive index lowering component that lowers the refractive index of the cured optical interference layer. The refractive index lowering component is, for example, in the form of particles (hereinafter, sometimes referred to as refractive index lowering particles).

[0165] An example of the refractive index lowering component is hollow silica fine particles. The hollow silica fine particles can lower the refractive index of the light interference layer while maintaining its strength. The hollow silica fine particles have a structure filled with gas and / or a porous structure containing gas. The refractive index decreases in inverse proportion to the occupancy rate of the gas. Therefore, the hollow silica fine particles have a refractive index lower than the original refractive index of the silica fine particles. An example of the hollow silica fine particles is Sururia 4320 (manufactured by JGC Catalysts).

[0166] As the refractive index lowering component, silica fine particles that form a nanoporous structure in at least a part of the interior and / or surface may be used. The nanoporous structure is formed depending on the morphology, structure, and aggregation state of the silica fine particles, and the dispersion state inside the coating film.

[0167] The average particle size of the refractive index-reducing particles is preferably 60 nm or more and 200 nm or less. The average particle size is the primary particle size.

[0168] The content of the refractive index lowering component is preferably 35 parts by mass or more and 70 parts by mass or less, and more preferably 37.5 parts by mass or more and 60 parts by mass or less, relative to 100 parts by mass of the solid content of the composition R. This makes it easier for the cured light interference layer to exhibit excellent antireflection properties.

[0169] The resin components of the composition HC and the composition R may be the same or different. In particular, it is preferable that the resin components of both are the same or of the same type. This is because the adhesion between the uncured hard coat layer and the uncured light interference layer is improved, and peeling between the layers is less likely to occur.

[0170] [Uncured functional layer] The laminated film may further have at least one uncured functional layer between the uncured hard coat layer and the uncured optical interference layer, which reinforces the optical function of the laminated film or imparts a new optical function to the laminated film.

[0171] The functional layer may be another optical interference layer having different optical properties from the optical interference layer described above. The functional layer may be a combination of two or more optical interference layers having different properties from the optical interference layer described above.

[0172] When the optical interference layer has a low refractive index, a preferable functional layer is, for example, at least one of an optical interference layer having a high refractive index and an optical interference layer having a medium refractive index.

[0173] The thickness of the other optical interference layer is not particularly limited. The thickness of each of the other optical interference layers may be 10 nm or more and 300 nm or less. The thickness of each of the optical interference layers is preferably 15 nm or more, more preferably 40 nm or more, and particularly preferably 60 nm or more. The thickness of each of the optical interference layers is preferably 200 nm or less, more preferably 180 nm or less, and particularly preferably 150 nm or less.

[0174] The functional layer forming composition forming the functional layer may contain the same components as those contained in the above composition HC or composition R. The functional layer forming composition forming the other light interference layer may contain the same components as those contained in composition R. The components contained in the multiple light interference layers may be the same or different. The resin components contained in the multiple light interference layers may be the same or different.

[0175] The high refractive index layer and the medium refractive index layer may contain a resin component other than the active energy ray curable type. Examples of the other resin components include thermoplastic resins such as alkyd resins, polyester resins, and acrylic resins; thermosetting resins such as epoxy resins, phenol resins, melamine resins, urethane resins, and silicone resins; and polyisocyanates.

[0176] [Protective film] The laminated film may have a protective film on the surface of the uncured light interference layer opposite to the uncured hard coat layer.

[0177] The protective film protects the light interference layer and the laminate film, and also functions as a release paper for forming the composition R into a film. The protective film may have an adhesive layer on the application surface.

[0178] Any protective film known in the art may be used without any particular limitation. The protective film may be colorless or colored. The protective film may be transparent.

[0179] 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 makes it easier to improve the protective effect of the uncured light interference layer. The thickness of the protective film is preferably 25 μm or more, more preferably 30 μm or more, even more preferably 33 μm or more, and particularly preferably 35 μm or more. The thickness of the protective film is preferably 85 μm or less, more preferably 80 μm or less, and even 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.

[0180] The protective film is made of, for example, a resin. Examples of the resin film include polyolefin films such as polyethylene films and polypropylene films (including unstretched polypropylene films (CPP films) and biaxially stretched polypropylene films (OPP films)), modified polyolefin films obtained by modifying these polyolefins and adding additional functions, polyester films such as polyethylene terephthalate, polycarbonate, and polylactic acid, polystyrene-based resin films such as polystyrene films, AS resin films, and ABS resin films, nylon films, polyamide films, polyvinyl chloride films, polyvinylidene chloride films, and polymethylpentene films.

[0181] If necessary, the resin film may contain additives such as an antistatic agent, an ultraviolet ray inhibitor, etc. The surface of the resin film may be subjected to a corona treatment or a low-temperature plasma treatment.

[0182] Among these, at least one film selected from the group consisting of polyethylene film, polystyrene film, modified polyolefin film, polymethylpentene film, OPP film and CPP film is preferred.

[0183] In particular, at least one film selected from the group consisting of polyethylene films, polystyrene films, modified polyolefin films, polymethylpentene films, OPP films and CPP films having a thickness of 30 μm or more and 100 μm or less is preferred.

[0184] B. Laminated material The laminated member according to the present embodiment is obtained by curing the laminated film. The laminated member is a completely cured product of the laminated film. The laminated member has a transparent support substrate, a cured hard coat layer, and a cured light interference layer in this order. The laminated member may further have at least one cured functional layer between the cured hard coat layer and the cured light interference layer. The laminated member may or may not further have a protective film. The protective film is used depending on the purpose of use.

[0185] The laminated member can be obtained, for example, by irradiating the laminated film with active energy rays to cure the uncured hard coat layer and the uncured light interference layer.

[0186] The laminated member is particularly suitable as a protective material for a display and various sensors arranged around the display. Examples of the display include a liquid crystal display, an organic electroluminescence display, and a plasma display. The laminated member is particularly suitable as a protective material for an in-vehicle touch panel display and its periphery. The laminated member is arranged so that the optical interference layer is on the outer side of the hard coat layer.

[0187] [Decorative layer] The laminated member may further include a decorative layer. The laminated member includes, for example, a transparent supporting substrate, a hard coat layer and a light interference layer disposed on one main surface of the transparent supporting substrate, and a decorative layer disposed on the other main surface of the transparent supporting substrate. 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 provides the laminated member with decoration such as a pattern, letters, or metallic luster. The decorative layer enhances the design of the laminated member.

[0188] The decorative layer may be, for example, at least one of a printed layer and a vapor deposition layer. Each of the printed layer and the vapor deposition layer is one or more layers, and may have 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.

[0189] The printed layer may have, for example, a wood grain pattern, a stone pattern, a cloth pattern, a sand pattern, a geometric pattern, letters, or a solid pattern. The printed layer may be formed, for example, from a colored ink containing a binder resin and a colorant. The binder resin is not particularly limited. Examples of the binder resin include polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose ester resins, alkyd resins, and chlorinated polyolefin resins.

[0190] The colorant is not particularly limited, and may be any known pigment or dye. Examples of yellow pigments include azo pigments such as polyazo, organic pigments such as isoindolinone, or inorganic pigments such as titanium nickel antimony oxide. Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, or inorganic pigments such as red iron oxide. Examples of blue pigments include organic pigments such as phthalocyanine blue, or inorganic pigments such as cobalt blue. Examples of black pigments include organic pigments such as aniline black. Examples of white pigments include inorganic pigments such as titanium dioxide.

[0191] The deposition layer is formed of at least one metal selected from the group consisting of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, etc., or an alloy or compound thereof.

[0192] [Molded resin layer] The laminated member may further include a molded resin layer. The molded resin layer supports the hard coat layer and the light interference layer together with the transparent supporting substrate. The laminated member includes, for example, a transparent supporting substrate, a hard coat layer and a light interference layer disposed on one main surface of the transparent supporting substrate, and a molded resin layer disposed on the other main surface of the transparent supporting substrate. The shape of the molded resin layer is not limited. Therefore, the design freedom of the laminated member is increased.

[0193] The resin forming the molded resin layer is not particularly limited. The molded resin layer includes, for example, a thermosetting resin and / or a thermoplastic resin. Examples of the thermosetting resin include phenolic resin, epoxy resin, melamine resin, urea resin, unsaturated polyester, and thermosetting polyimide. Examples of the thermoplastic resin include so-called engineering plastics. Examples of the engineering plastic include polyamide, polyacetal, polycarbonate, ultra-high molecular weight polyethylene, polysulfone, polyethersulfone, polyphenylene sulfide, and liquid crystal polymer.

[0194] The laminated member may include a transparent supporting substrate, a hard coat layer and a light interference layer disposed on one main surface of the transparent supporting substrate, a decorative layer disposed on the other main surface of the transparent supporting substrate, and a molded resin layer. In this case, the decorative layer is disposed so as to be sandwiched between the transparent supporting substrate and the molded resin layer.

[0195] [Manufacturing method for laminated members] The laminated member according to the present embodiment is manufactured by a method including, for example, a step of preparing the laminated film and a step of irradiating the laminated film with active energy rays. After the step of preparing the laminated film, a decorating step, a preforming step, and a main molding step are performed as necessary. The decorating step is preferably performed before the preforming step.

[0196] The step of irradiating the active energy rays may be carried out multiple times. For example, after the decorating step and / or the preforming step, a semi-curing step may be carried out in which the active energy rays are irradiated so as to cure a part of the laminated film. In this case, after the main molding step, a main curing step is carried out in which the active energy rays are irradiated so as to cure the remaining part of the laminated film.

[0197] The type of active energy rays is not particularly limited. The active energy rays are appropriately selected depending on the type of resin component contained in the layer-forming composition. The active energy rays are not particularly limited, and may be ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among them, ultraviolet rays having a wavelength of 380 nm or less are preferred. The ultraviolet rays are irradiated using, for example, a high-pressure mercury lamp or an ultra-high-pressure mercury lamp.

[0198] (1) Laminated film preparation process A laminate film is prepared. The laminate film has a transparent supporting substrate, an uncured hard coat layer formed on at least one surface of the transparent supporting substrate, and an uncured optical interference layer formed on the uncured hard coat layer.

[0199] The laminate film is produced by a method including the steps of forming an uncured hard coat layer on at least one surface of a transparent supporting substrate, and laminating an uncured optical interference layer on the uncured hard coat layer.

[0200] (1-1) Step of forming an uncured hard coat layer The method of forming the uncured hard coat layer is not particularly limited. The uncured hard coat layer is formed, for example, by applying the composition HC to at least one surface of the transparent support substrate. After application, a drying process may be performed. The drying conditions are not particularly limited, and are appropriately set so that at least a part of the solvent contained in the composition HC is removed.

[0201] Composition HC can be prepared by a method commonly used by those skilled in the art, for example, by mixing the above-mentioned components using a commonly used mixing device such as a paint shaker or mixer.

[0202] The method of applying the composition HC is not particularly limited, and can be performed by a method commonly used by those skilled in the art. Examples of the application method include dip coating, air knife coating, curtain coating, roller coating, bar coating (e.g., wire bar coating), die coating, inkjet coating, gravure coating, and extrusion coating (U.S. Patent No. 2,681,294).

[0203] (1-2) Step of Laminating an Uncured Hard Coat Layer and an Uncured Light Interference Layer The method for laminating the uncured hard coat layer and the uncured light interference layer is not particularly limited, and may be a coating method or a lamination method.

[0204] In the coating method, the composition R is applied onto the uncured hard coat layer to laminate the uncured optical interference layer. After the application, a drying step may be performed. The drying conditions are not particularly limited and are appropriately set so that at least a part of the solvent contained in the composition R is removed.

[0205] The other functional layer forming composition is applied on the uncured hard coat layer by the above method before applying composition R on the uncured hard coat layer. This results in a laminated film in which the uncured other functional layer is disposed between the uncured hard coat layer and the uncured light interference layer. The other functional layer forming composition and composition R can be prepared by the above method.

[0206] In the lamination method, an uncured optical interference layer formed on another supporting substrate (typically, the above-mentioned protective film) and an uncured hard coat layer formed on a transparent supporting substrate are laminated together. In this case, the interphase between the uncured hard coat layer and the uncured optical interference layer is particularly easily suppressed.

[0207] The uncured optical interference layer is formed by applying composition R onto another supporting substrate. The composition R is applied by a method commonly used by those skilled in the art, similar to the composition HC. After application, a drying step may be performed. After the two are bonded together, the other supporting substrate may be peeled off.

[0208] Other functional layers may also be laminated by lamination. The other functional layer is laminated, for example, by the following process. From the laminate obtained by the above lamination process, which includes a transparent supporting substrate, an uncured hard coat layer, an uncured light interference layer (first light interference layer), and the other supporting substrate in this order, the other supporting substrate is peeled off to expose the uncured light interference layer. Separately, the other uncured functional layer is formed on a new supporting substrate. Next, an uncured functional layer supported by the new supporting substrate is laminated to the exposed uncured light interference layer. These processes may be repeated as necessary.

[0209] (2) Decoration process When the hard coat layer is disposed on one main surface of the transparent support substrate, the above-mentioned decorative layer may be formed on the other main surface of the transparent support substrate before the forming step. The decorative step may be performed before the preparation step or after the preparation step. From the viewpoint of productivity, it is preferable that the decorative step is performed after the preparation step.

[0210] The method for forming the printed layer is not particularly limited. Examples of the method for forming the printed layer include offset printing, gravure printing, screen printing, roll coating, and spray coating. The method for forming the vapor deposition layer is also not particularly limited. Examples of the method for forming the vapor deposition layer include vacuum deposition, sputtering, ion plating, and plating.

[0211] (3) Preforming process When manufacturing a laminated member having a three-dimensional shape, the laminated film may be molded into a shape according to the desired three-dimensional shape after the preparation process (and further the decoration process) and before the main molding process. By molding the laminated film into a shape close to the three-dimensional shape in advance, it becomes easier to further suppress the occurrence of cracks, wrinkles, etc. when molding into a three-dimensional shape thereafter. After the preforming process, a trimming process may be performed to remove unnecessary parts of the laminated film.

[0212] The method of preforming is not particularly limited. Preforming is performed by, for example, vacuum forming, pressure forming, or vacuum pressure forming. In preforming, a mold and a laminated film are placed in the same processing chamber. The laminated film is placed so that the transparent support substrate faces the mold. The laminated film is heated to put the processing chamber into a vacuum state and / or a pressurized state. This causes the laminated film to deform along the mold. The laminated film is then cooled and removed from the mold.

[0213] During preforming, the laminated film may be heat-treated at a temperature of 90° C. or more and 150° C. or less. The laminated film according to the present embodiment is not easily hardened by heat treatment, so that the elongation ratio is not easily reduced, while the surface of each layer can be made smooth.

[0214] (4) Semi-curing process Before the main molding step, the laminated film may be irradiated with active energy rays so as to be partially cured, thereby obtaining a laminated film in a semi-cured state.

[0215] The semi-curing step is usually carried out after the preforming step. The semi-curing step makes it possible to obtain the stretching ratio required for the preforming step and / or the main molding step. The integrated light amount of the active energy rays is, for example, 1 mJ / cm 2 More than 100mJ / cm 2 After the semi-curing step, a trimming step may be carried out to remove unnecessary portions of the laminated film.

[0216] (5) Main molding process In this molding step, for example, insert molding is performed. In the insert molding method, for example, the optical interference layer is placed opposite a metal mold, and a molding resin is injected toward the transparent support substrate. As a result, the laminated film is shaped into a three-dimensional shape, and a molding resin layer is formed on the other main surface of the transparent support substrate.

[0217] (6) Main curing process The laminated film is irradiated with active energy rays to completely cure the laminated film. This results in a laminated member. The integrated light amount of the active energy rays is, for example, 100 mJ / cm. 2 That's all. The cumulative amount of active energy rays is 5000mJ / cm 2 or less than 3000 mJ / cm 2 The active energy rays may be the same as or different from those in the semi-curing step.

[0218] The above-mentioned embodiment is merely an example, and known treatments, processing steps, etc. may be introduced as desired. EXAMPLES

[0219] 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 by weight unless otherwise specified.

[0220] The components used in the examples and comparative examples in this specification are as follows. (Reactive acrylic resin) (1) Product name: KRM-9322, manufactured by Daicel Olenex Co., Ltd., Tg: 60°C, Mw: 50,000 (2) Product name: WEL-355, manufactured by DIC, Tg: 85°C, Mw: 45,000

[0221] (Multifunctional urethane acrylate oligomer) Product name: KRM-8452, Daicel Allnex, Mw: 3884, Acrylate equivalent: 120g / eq

[0222] (Fluorine-containing polyfunctional silicone acrylate oligomer) Product name: Shiko UV-AF305, manufactured by Mitsubishi Chemical Corporation, Mw: 18000

[0223] (Multifunctional urethane acrylate oligomer) Product name: H-7M40, manufactured by Negami Kogyo Co., Ltd., Mw: 10000~15000

[0224] (Multifunctional urethane acrylate oligomer) Product name: CN-9893, manufactured by Arkema

[0225] (Multifunctional acrylate oligomer) Product name: Aronix M-315, manufactured by Toagosei Co., Ltd., Mw: 450, acrylate equivalent: 150g / eq

[0226] (Refractive index decreasing component) Product name: Sururia 4320, manufactured by JGC Catalysts, hollow silica particles

[0227] (Inorganic oxide fine particles) (1) Product name: OSCAL 1842, manufactured by JGC Catalysts and Chemicals Industries, particle size 10 nm, reactive silica organosol (2) Product name: HX-204 IP, Nissan Chemical Co., Ltd., phosphorus-doped tin oxide sol, particle size 5 nm to 20 nm

[0228] (Photopolymerization initiator) Product name: Omnirad 184, IGM RESINS, α-hydroxyalkylphenone

[0229] (Transparent support base material) TB1-TB4: ​​Product name AW-10U, manufactured by Wavelock Advanced Technology Co., Ltd., two-layer (PMMA / PC) film made of PMMA and PC, TB1: thickness 300 μm, TB2: thickness 200 μm, TB3: thickness 500 μm, TB4: thickness 800 μm, TB5: thickness 100 μm

[0230] (Protective film) Product name: Torayfan #40-2500, Toray Industries, biaxially oriented polypropylene film (OPP), thickness 40 μm

[0231] [Preparation of Composition HC1] A transparent composition HC1 with a solids concentration of 35% was prepared by mixing 47.6 parts by mass of KRM-9322 (reactive acrylic resin), 33.3 parts by mass of KRM-8452 (multifunctional urethane acrylate oligomer), 14.3 parts by mass of OSCAL 1842 (inorganic oxide fine particles), and 4.8 parts by mass of Omnirad184 (photopolymerization initiation) in a container containing 185 parts of methyl isobutyl ketone.

[0232] [Preparation of Compositions HC2-HC6] Transparent compositions HC2-HC6 each having a solid content of 35% were prepared in the same manner as composition HC1, except that the formulations were as shown in Table 1C.

[0233] [Preparation of Composition LR1] In a container containing 1203 parts of propylene glycol monomethyl ether, 24.8 parts by mass of KRM-9322 (reactive acrylic resin), 13.3 parts by mass of KRM-8452 (multifunctional urethane acrylate oligomer), 13.3 parts by mass of SHIKO UV-AF305 (multifunctional silicon acrylate oligomer containing fluorine atoms), and 4.8 parts by mass of Omnirad184 (photopolymerization initiation) were mixed. Furthermore, 43.8 parts by mass of Suluria 4320 (refractive index reducing component) were mixed. This resulted in the preparation of a transparent composition LR1 with a resin solid content concentration of 3.0%.

[0234] [Preparation of compositions LR2-LR5] Transparent compositions LR2 to LR5 each having a solid content of 35% were prepared in the same manner as composition LR1, except that the formulations shown in Table 1A were used.

[0235] [Preparation of other functional layer-forming compositions HR1 and MR1] Other transparent functional layer-forming compositions HR1 and MR1, each having a solid content concentration of 35%, were prepared in the same manner as composition LR1, except that the formulations shown in Table 1B were used.

[0236] [Example 1] (1) Manufacturing of laminated films (1-1) Formation of an uncured hard coat layer Composition HC1 was applied to the PMMA surface of transparent supporting substrate TB1 by a gravure coater so that the thickness after drying would be 8 μm. Then, the composition was dried at 80° C. for 1 minute to volatilize the solvent, thereby forming an uncured hard coat layer.

[0237] The surface of the uncured hard coat layer thus obtained was subjected to a finger touch test, and then the appearance was observed. There was no change in the appearance of the surface of the uncured hard coat layer, and it could be evaluated as being tack-free. Hereinafter, the hard coat layer may be referred to as an "HC layer."

[0238] (1-2) Formation of an uncured optical interference layer Composition LR1 was applied to an OPP film (protective film) by a gravure coater so that the thickness after drying was 95 nm. Then, the film was dried at 80°C for 1 minute to volatilize the solvent, forming an uncured light interference layer. The surface of the obtained uncured light interference layer was also tack-free. The protective film on which the uncured light interference layer was formed was wound into a roll. Hereinafter, the optical interference layer formed from the composition LR1 having a low refractive index may be referred to as an "LR layer."

[0239] (1-3) Lamination of uncured HC layer and LR layer While unwinding the rolled protective film, the uncured HC layer surface supported by the transparent supporting substrate TB1 was laminated to the uncured LR surface supported by the protective film, thereby producing a laminated film having the transparent supporting substrate, the uncured HC layer, the uncured LR layer, and the protective film in this order.

[0240] (2) Manufacturing of laminated members (2-1) Formation of the printing layer A printed layer was formed by screen printing on the surface of the transparent support substrate of the laminated film opposite the uncured HC layer, and dried at a drying temperature of 80°C for 10 minutes. This printing process was repeated five times, and then dried at 90°C for 1 hour. A black paint (product name: CZ-805 BLACK (manufactured by Nikko Vicks Co., Ltd.) was used to form the printed layer.

[0241] (2-2) Peeling off the protective film The protective film was then peeled off from the uncured LR layer at a speed of 5.0 mm / sec.

[0242] (2-3) Preform The laminated film with the printed layer was heated at 190° C. for 30 seconds, and a preform was formed by vacuum and pressure molding.

[0243] (2-4) Main curing Accumulated light dose of 500mJ / cm2 on preformed laminated film 2 The specimen was then irradiated with active energy rays of 1000 .mu.m. Then, trimming was carried out.

[0244] (2-5) Main molding Finally, injection molding was performed to obtain a laminated member having a molded resin layer (polycarbonate) on the printed layer side of the transparent support substrate. In the examples, unless otherwise specified, ultraviolet light was used as the active energy ray.

[0245] [evaluation] The laminated film and laminated member were subjected to the following evaluations. (a) Refractive index Compositions LR1 to LR5, HR1 and MR1 were each applied onto a protective film so that the dry thickness was 5 μm. Then, the coating film was exposed to an integrated light dose of 500 mJ / cm 2 The sample was irradiated with active energy rays of 1000 nm to prepare an evaluation sample. The refractive index of the evaluation sample was measured at D line 589 nm using an Atago Co., Ltd. Appe Refractometer DR-M2. The evaluation sample was set on the prism surface, and 1-bromonaphthalene was used as the intermediate liquid.

[0246] (b) Thickness An evaluation sample of 10 mm x 10 mm was cut out from the laminated member. The cross section of the evaluation sample was precipitated with a microtome (LEICA RM2265). The precipitated cross section was observed with a laser microscope (VK8700, manufactured by KEYENCE) or a transmission electron microscope (JEM2100, manufactured by JEOL Ltd.), and the thicknesses of 10 points of the HC layer and LR layer were measured. The average values ​​were regarded as the thicknesses of the HC layer and the LR layer, respectively.

[0247] (c) Luminous reflectance A black paint (product name: CZ-805 BLACK (manufactured by Nikko Bix Co., Ltd.) was applied to the surface of the transparent support substrate of the laminated film opposite the uncured HC layer using a bar coater so that the dry film thickness was 3 μm to 6 μm. Next, the laminated film coated with the black paint was left to dry in a room temperature environment for 5 hours to prepare an uncured evaluation sample.

[0248] The luminous reflectance of the evaluation sample was measured from the light interference layer side by the SCI method using SD7000 manufactured by Nippon Denshoku Industries Co., Ltd., in a measurement wavelength range of 380 nm to 780 nm.

[0249] (d) Stretching rate A test piece measuring 200 mm in length and 10 mm in width was cut out from the laminated film. This test piece was set in a tensile tester with a chuck distance of 150 mm, and the long side of the evaluation sample was stretched by 50% under conditions of a tensile force of 5.0 kgf and a tensile speed of 300 mm / min in an atmosphere of 160°C. The evaluation sample after stretching was observed using a microscope with a magnification of 1000 times or more to confirm the presence or absence of cracks exceeding 100 μm in length and 1 μm in width.

[0250] If no cracks were found, a new evaluation sample was cut out and the long side was stretched by 60%. The same procedure was then used to observe whether cracks were found. This procedure was repeated while increasing the stretch ratio by 10% each time. The stretch ratio at which a crack of the above size was first observed was taken as the stretch ratio of the laminated film. The above evaluation was carried out three times for evaluation samples cut out from the same laminated film, and the average stretch ratio obtained each time was taken as the stretch ratio of the laminated film.

[0251] (e) Paint film hardness The hardness was measured from the uncured LR layer side of the laminated film and the LR layer side of the laminated member. The hardness was measured by a continuous stiffness measurement method (method used: Advanced Dynamic E and H.NMT) using an iMicro Nanoindenter manufactured by NANOMECHANICS, INC.

[0252] Specifically, a minute AC load was superimposed on a quasi-static test load and applied to the surface of the evaluation sample. The load was applied until it reached a maximum load of 50 mN. A Berkovich-type diamond indenter (tip curvature radius 20 nm) was used as the indenter. Continuous stiffness with respect to depth was calculated from the vibration component of the generated displacement and the phase difference between the displacement and the load, and a profile of hardness with respect to depth was obtained. The maximum hardness was calculated from this profile at depths of 50 nm to 100 nm.

[0253] The load and stiffness were calculated using iMicro's dedicated software. When calculating 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. When analyzing with iMicro's dedicated software, the surface position of the coating layer was set to the point provisionally defined in the iMicro dedicated software during measurement (the point where d(Force) / d(Disp) is approximately 500N / m).

[0254] (f) Handling after preforming Accumulated light dose of 500mJ / cm on preformed laminated film 2 The evaluation sample was irradiated with active energy rays of 1000 rpm to obtain an evaluation sample. The evaluation sample was evaluated for handleability when being set in a metal mold for injection molding. The evaluation criteria are as follows: Good: The evaluation sample has firmness and can be easily placed in the injection mold. Pass: The evaluation sample is weak and slightly difficult to handle, but can be placed in the mold. Poor: The evaluation sample was weak and could not be placed in the mold.

[0255] (g) Warping of laminated members A 200mm x 200mm evaluation sample was cut out from the laminated film and exposed to an accumulated light dose of 500mJ / cm 2 Next, the evaluation sample was placed on a horizontal surface, and the amount of lift (amount of warping) of the four corners from the horizontal surface was measured using a ruler and averaged. The evaluation criteria are as follows: Best: Average warpage is 10mm or less Good: Average warpage is 10 to less than 15 mm Acceptable: Average warpage is 15mm or more and less than 20mm Defective: Average warpage is 20mm or more

[0256] (h) Appearance after printing process After peeling off the protective film (2-2), the laminated film before preforming (2-3) was used as an evaluation sample. The evaluation sample was visually inspected for the presence or absence of squeegee marks and suction marks caused by the printing process. The evaluation criteria are as follows: Best: No squeegee or suction marks Good: There are slight squeegee marks and suction marks, but they level out and disappear when heated to 90°C or higher. Acceptable: There are slight squeegee marks and suction marks, but they level out and disappear when heated to 150°C or higher. Defective: Squeegee marks and suction marks

[0257] (i) Adhesion between uncured HC layer and LR layer A laminate film of a transparent supporting substrate and an uncured hard coat layer and a laminate film of a protective film and an uncured light interference layer were bonded together while being pressed with a hand roller so that the layers faced each other, and the degree of bonding was evaluated. The evaluation criteria are as follows: Good: Films are stuck together Possible: The films are stuck together, but the adhesion is weak. Defective: The film is not attached to each other at all.

[0258] (j)Pencil hardness The pencil hardness of the LR layer of the laminate was evaluated. The measurement was carried out in accordance with JIS K5600-5-4 (1999), scratch hardness (pencil method).

[0259] (k) Abrasion resistance The surface of the LR layer of the laminated member was rubbed 5000 times with a friction element to which cotton cloth was fixed while applying a vertical load of 4.9 N. The surface of the LR layer of the laminated member was visually observed. The surface of the LR layer of the laminated member was then rubbed until the cumulative number of times reached 7000. The surface of the LR layer of the laminated member was visually observed. The evaluation criteria were as follows: Best: No visible scratches even after 7000 rubs Good: No visible scratches after 5000 rubs, but visible scratches after 7000 rubs Acceptable: After 5,000 rubs, 5 or fewer scratches were visible Bad: Many scratches were visible after 5,000 rubs

[0260] (l) Chemical resistance An evaluation sample of 10 cm x 10 cm was cut out from the laminated member. 2 g of Neutrogena Sunscreen SPF45 (manufactured by Johnson & Johnson) was evenly applied to the entire surface of the LR layer of the evaluation sample with a finger. The sample was then heated at 80°C for 4 hours. The sample was then cooled to room temperature and washed with water, and the appearance of the LR layer was visually evaluated. The evaluation criteria are as follows: Best: No abnormalities in appearance Good: Traces of application are visible, but no lifting is observed Acceptable: Slight lifting observed Bad: Severe lifting is occurring

[0261] [Examples 2 to 17] In the same manner as in Example 1, a laminate film and a laminate member having the configuration shown in Tables 2A and 2B were prepared using compositions prepared according to the formulations shown in Tables 1A, 1B, and 1C. The obtained laminate film and laminate member were evaluated in the same manner as in Example 1. The results are shown in Tables 2A and 2B. In each of the examples, the surfaces of the obtained uncured hard coat layer and light interference layer were tack-free.

[0262] [Comparative Example 1] An uncured HC layer was formed on a transparent supporting substrate TB1 in the same manner as in Example 1, except that composition HC4 was used. Then, the HC layer was irradiated with an integrated light dose of 500 mJ / cm 2 2 The HC layer was cured by irradiating it with active energy rays. Composition LR3 was applied to the cured HC layer. Composition LR3 was then dried to form an LR layer with a dry thickness of 95 nm. Finally, an integrated light dose of 500 mJ / cm was applied. 2A pre-cured laminate film was obtained by irradiating the laminate film with active energy rays of 1000 .mu.m. This laminate film was used to prepare a laminate member in the same manner as in Example 1, and evaluated. The results are shown in Table 3.

[0263] [Comparative Example 2] Except for not forming the uncured LR layer, a laminate film and a laminate member were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0264] [Comparative Example 3] Except for using composition LR4 instead of composition LR1, a laminated film was obtained in the same manner as in Example 1. Using this laminated film, a laminated member was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0265] [Comparative Example 4] Instead of the transparent supporting substrate TB1, TB4 was prepared, and an uncured hard coat layer was formed in the same manner as in Example 1. However, because the transparent supporting substrate TB4 was too thick, the uncured hard coat layer and the uncured light interference layer were not properly bonded together, and a laminated film could not be produced. Therefore, it was not possible to produce and evaluate a laminated member.

[0266] [Comparative Examples 5 and 6] Except for changing the thickness of the uncured light interference layer, laminate films and laminate members were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0267] [Table 1A]

[0268] [Table 1B]

[0269] [Table 1C]

[0270] [Table 2A]

[0271] [Table 2B]

[0272] [Table 3]

[0273] As can be seen from Tables 2A and 2B, the laminated film according to this embodiment can be molded into complex shapes and further suppresses the occurrence of defective products during molding. In addition, the laminated member according to this embodiment has excellent hard coat performance (e.g., high hardness, abrasion resistance, chemical resistance, etc.) and excellent antireflection properties.

[0274] The laminated film of Comparative Example 1 is a pre-cured type. Therefore, each layer is composed of a composition that allows three-dimensional molding after curing. Therefore, the crosslink density of the composition after curing is low, and the abrasion resistance and chemical resistance are poor.

[0275] The laminate films of Comparative Examples 2, 3, 5 and 6 have high luminous reflectance and are poor in antireflection performance. [Industrial Applicability]

[0276] According to the present invention, a laminated film that can be formed into a complex shape can be provided, and therefore, this laminated film is particularly suitable for use in producing a protective material for a display.

[0277] This application claims priority based on Japanese Patent Application No. 2019-138313, filed on July 26, 2019, the entire contents of which are incorporated herein by reference.

Claims

1. A transparent support substrate; an uncured hard coat layer formed on at least one surface of the transparent support substrate; an uncured optical interference layer formed on the uncured hard coat layer; a protective film disposed on a surface of the uncured light interference layer opposite to the uncured hard coat layer, The uncured hard coat layer contains an active energy ray-curable hard coat layer-forming composition, the uncured light interference layer contains an active energy ray-curable light interference layer-forming composition, The thickness of the transparent support substrate is 50 μm or more and 600 μm or less, a luminous reflectance including specular reflection light measured from the uncured light interference layer side of the laminate film after peeling off the protective film is 0.1% or more and 4.0% or less; The stretch ratio of the laminated film at 160° C. after peeling off the protective film is 50% or more, the hardness of the laminate film measured by a nanoindentation method from the uncured light interference layer side after the protective film is peeled off is 0.1 GPa or more and 0.5 GPa or less; The uncured hard coat layer and the uncured light interference layer have not been exposed to actinic energy rays or have been exposed to less than 1 mJ / cm ２ A laminated film that has been exposed to actinic radiation of less than 1000 nm.

2. The laminate film according to claim 1 , wherein the uncured optical interference layer has a thickness of 15 nm or more and 200 nm or less.

3. 3. The laminated film according to claim 1, wherein the uncured hard coat layer has a thickness of 2 μm or more and 30 μm or less.

4. After peeling off the protective film, the accumulated light amount is 500 mJ / cm ２ The laminate film according to claim 1 , wherein the hardness measured by a nanoindentation method from the light interference layer side of the laminate film irradiated with active energy rays is more than 0.5 GPa and not more than 1.2 GPa.

5. The protective film is peeled off, and then the laminated film is irradiated with an integrated light dose of 500 mJ / cm ２ 5. The laminate film according to claim 1 , wherein when the surface of the light interference layer is rubbed 5,000 times while applying a normal load of 4.9 N after irradiation with active energy rays, no scratches are visible on the light interference layer.

6. The laminate film according to claim 1 , further comprising at least one uncured functional layer between the uncured hard coat layer and the uncured light interference layer.

7. A laminated member comprising a laminated film described in any one of claims 1 to 6 that has been hardened after the protective film has been peeled off.

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