Laminated films and molded articles and their manufacturing methods

Abstract

A post-cured laminated film with low reflectivity is provided. The laminated film comprises a transparent support substrate, an uncured hard coating layer formed on at least one surface of the transparent support substrate, and an uncured optical interference layer formed on the uncured hard coating layer. The uncured hard coating layer contains an active energy line curable hard coating forming composition, and the uncured optical interference layer contains an active energy line curable optical interference layer forming composition. The thickness of the transparent support substrate is 50 μm or more and 600 μm or less. The laminated film has a tensile strength of 50% or more at 160°C. The minimum reflectivity R of the laminated film measured from the uncured optical interference layer side at wavelengths between 380 nm and 780 nm after heat treatment at 90°C for 30 minutes is... AH It is below 2%.

Description

Technical Field

[0001] This invention relates to laminated films and molded articles, as well as methods for manufacturing them. Background Technology

[0002] Displays are used in a wide variety of fields, including computers, televisions, mobile phones, portable information terminal devices (tablets, mobile devices, and electronic notebooks, etc.), as well as in-vehicle display panels such as digital instruments, dashboards, navigation systems, control panels, central instrument clusters, and heater control panels. Such products are often covered with protective materials. These protective materials are typically obtained by molding a film with a hard coating.

[0003] In protective materials for displays, a low-refractive-index layer is sometimes provided to reduce the reflectivity of the viewing side surface. Patent Document 1 shows a laminated film in which a hard coating layer and a low-refractive-index layer (optical interference layer) are sequentially stacked on a transparent support.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent document 1: Japanese Patent Application Publication No. 2015-004937. Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] In recent years, various decorative layers have been incorporated into the protective film material of displays, or the protective material of displays has been molded into three-dimensional shapes, depending on the intended use and design. However, if a heating process is performed, the reflectivity of the laminated film may sometimes increase.

[0009] The present invention was made to solve the above-mentioned existing problems, and its object is to provide post-cured laminated films and molded articles with low reflectivity, as well as methods for manufacturing them.

[0010] Methods for solving problems

[0011] To address the aforementioned issues, the present invention provides the following approach.

[0012] Laminated membranes, which possess the following characteristics:

[0013] Transparent support substrate

[0014] An uncured hard coating formed on at least one surface of the transparent support substrate, and

[0015] An uncured optical interference layer is formed on the uncured hard coating.

[0016] The uncured hard coating contains an active energy line curing type hard coating forming composition.

[0017] The uncured optical interference layer contains an active energy line-cured optical interference layer forming composition.

[0018] The thickness of the transparent support substrate is 50 μm or more and 600 μm or less.

[0019] The laminated film has an elongation of more than 50% at 160°C.

[0020] The minimum reflectance R of the laminated film after heat treatment at 90°C for 30 minutes, measured from the uncured optical interference layer side, between wavelengths of 380 nm and 780 nm. AH It is below 2%.

[0021] According to the laminated film described above [1], wherein the minimum value of the reflectivity R AH The minimum value R of the reflectance of the laminated film before heat treatment, measured from the uncured optical interference layer side, between wavelengths of 380 nm and 780 nm. BH The following relationship must be satisfied:

[0022] 100×|R AH -R BH | / R BH ≤20 (%).

[0023] According to the laminated film described in [1] or [2] above, wherein,

[0024] The optical interference layer forming composition contains a first layer forming component and low-refractive particles.

[0025] The first layer forming component contains a first reactive component having two or more polymerizable functional groups in one molecule.

[0026] The first reactive component contains at least one selected from a first polymer with a weight average molecular weight greater than 10,000, a first oligomer with a weight average molecular weight less than 10,000, and a first monomer with a weight average molecular weight less than 10,000.

[0027] The content X of the low-refractive particles, the total content Y of the first oligomer and the first monomer, and the content Z of the first polymer satisfy the following relationship:

[0028] X + Y + Z = 100,

[0029] X≥30,

[0030] Y≥0,

[0031] Z≥0, and

[0032] Z≤1 / 2X-15.

[0033] The laminated film according to any one of [1] to [3] above, wherein,

[0034] The hard coating forming composition contains a second layer forming component.

[0035] The second layer forming component contains a second reactive component having two or more polymerizable functional groups in one molecule.

[0036] The second reactive component contains at least one of a second oligomer with a weight average molecular weight of less than 10,000 and a second monomer with a weight average molecular weight of less than 10,000.

[0037] According to the laminated film described above [4], the second reactive component further contains a second polymer with a weight-average molecular weight of more than 10,000.

[0038] According to the laminated film described in [4] or [5] above, the total content of the second oligomer and the second monomer is 25 parts by mass or more and 65 parts by mass or less, relative to 100 parts by mass of the solid components of the hard coating forming composition.

[0039] The laminated film according to any one of [1] to [6] above, wherein at least one uncured functional layer is further provided between the uncured hard coating layer and the uncured optical interference layer.

[0040] According to any one of the above [1] to [7], the hardness H measured from the uncured optical interference layer side by nanoindentation method is... BC The range is above 0.1 GPa and below 0.5 GPa.

[0041] According to any one of the above [1] to [8], the laminated film, wherein the cumulative light intensity irradiated is 2000 mJ / cm 2 The hardness H of the optical interference layer side of the stacked film with active energy lines was measured by nanoindentation. AC The range is above 0.25 GPa and below 0.7 GPa.

[0042] The laminated film according to any one of [1] to [9] above, wherein the thickness of the uncured hard coating is 2 μm or more and 30 μm or less.

[0043] According to any one of the above [1] to

[10] , the thickness of the uncured optical interference layer is 15 nm or more and 200 nm or less.

[0044] A molded body, wherein the molded body contains a cured laminated film according to any one of [1] to

[11] above.

[0045] According to the molded body described above

[12] , wherein,

[0046] The hard coating is disposed on one main surface of the transparent support substrate.

[0047] The molded body also has a decorative layer disposed on another main surface of the transparent support substrate.

[0048] The molded body described above

[13] further comprises a molding resin layer covering at least a portion of the decorative layer.

[0049] A method for manufacturing laminated films, comprising:

[0050] The process of forming an uncured hard coating by coating an active energy line curing type hard coating composition on one surface of a transparent support substrate with a thickness of 50 μm or more and 600 μm or less.

[0051] The process of forming an uncured optical interference layer by coating an active energy line-curing optical interference layer onto one side of another supporting substrate, and

[0052] A lamination process is performed by bonding the side of the uncured hard coating opposite to the transparent support substrate and the side of the uncured optical interference layer opposite to the other support substrate to obtain a laminated film.

[0053] The laminated film has an elongation of more than 50% at 160°C.

[0054] The minimum value R of the reflectance of the laminated film after heating at 90°C for 30 minutes, measured from the uncured optical interference layer side, between wavelengths of 380 nm and 780 nm. AH It is below 2%.

[0055] The method for manufacturing a molded body includes:

[0056] The decorative process of forming a decorative layer on another main surface of the transparent support substrate of the laminated film according to any one of [1] to

[11] above, and

[0057] A curing process that involves irradiating the laminated film with active energy lines after the decoration process;

[0058] The decorative process includes a heating process of heating the laminated film at a temperature above 80°C for more than 20 minutes.

[0059] According to the manufacturing method of the molded body described above

[16] , after the decoration process, there is an injection molding process in which the light interference layer is oriented toward the mold and a molding resin is injected into the decoration layer.

[0060] According to the manufacturing method of the molded body described above

[17] , the mold imparts a three-dimensional shape to the laminated film.

[0061] After the decoration process and before the injection molding process, a pre-forming process is performed to shape the laminated film into a shape according to the three-dimensional shape.

[0062] The effects of the invention

[0063] According to the present invention, post-cured laminates and molded articles having low reflectivity, as well as methods for manufacturing them, can be provided. Attached Figure Description

[0064] [ Figure 1 The diagram schematically shows a cross-sectional view of a laminated film according to one embodiment of the present invention.

[0065] [ Figure 2 The diagram schematically shows a cross-sectional view of a molded body according to one embodiment of the present invention.

[0066] [ Figure 3 This diagram shows a flowchart of a method for manufacturing a laminated film according to one embodiment of the present invention.

[0067] [ Figure 4 [A schematic diagram illustrating the lamination process in a method for manufacturing a laminated film according to one embodiment of the present invention.]

[0068] [ Figure 5 This diagram shows a flowchart of a method for manufacturing a molded article according to one embodiment of the present invention.

[0069] [ Figure 6 The flowchart illustrates a method for manufacturing a molded article according to another embodiment of the present invention. Detailed Implementation

[0070] As a protective film for displays, a type of laminated film known as pre-cured is typically used. As shown in Patent Document 1, in a pre-cured laminated film, each layer is cured during pre-forming. Therefore, in injection molding to a three-dimensional shape or in pre-forming prior to that, the laminated film cannot follow the mold of a deep three-dimensional shape, sometimes resulting in cracks or whitening in the laminated film.

[0071] To enable pre-cured laminated films to conform to deep, three-dimensional molds, a reduction in the crosslinking density of the laminated film was considered, which would decrease the hardness after curing. However, if the crosslinking density is low, it is difficult to obtain sufficient mechanical properties or chemical resistance.

[0072] To increase the crosslinking density of the laminated film as the final product while allowing it to conform to a mold with a deep three-dimensional shape, the laminated film can be cured after preforming. Such a laminated film is called a post-cured type. Post-cured laminated films have an uncured hard coating layer and an uncured optical interference layer.

[0073] In the case of post-curing laminated films, heat treatment performed during the formation of the decorative layer on the laminated film can sometimes cause phase mixing at the interface between the uncured hard coating and the optical interference layer. If phase mixing occurs at this interface, the reflectivity increases.

[0074] Therefore, in this embodiment, a laminated film exhibiting low reflectivity even after heat treatment is proposed. Specifically, the minimum reflectivity R of the laminated film after heat treatment at 90°C for 30 minutes, measured at wavelengths between 380 nm and 780 nm from the uncured optical interference layer side, is described. AH The reflectance is less than 2%. Therefore, the laminated film according to this embodiment can be decorated or shaped into complex forms while maintaining low reflectivity.

[0075] The laminated film is post-cured and has a tensile strength of over 50% at 160°C. Therefore, it suppresses cracking or whitening during preforming or injection molding processes, resulting in a good appearance of the molded product. Because cracking is difficult to occur, the functions of the hard coating and the optical interference layer can be utilized more effectively. Furthermore, since the laminated film has a tensile strength of over 50% at 160°C, and the thickness of the transparent support substrate is over 50 μm and under 600 μm, the resulting molded body possesses sufficient rigidity even when molded into complex shapes.

[0076] During preforming, the laminated film is stretched. In the case of post-curing laminated films, the preformed laminated film is in an uncured state. In other words, the uncured laminated film is stretched, and excessive stretching is not performed after curing. Therefore, each layer can be formed from the lamination composition in a manner that increases the crosslinking density. That is, the hardness of each layer after curing can be higher.

[0077] Furthermore, since neither the hard coating nor the optical interference layer is cured during lamination, the interlayer adhesion is enhanced. Additionally, heat treatment allows for surface leveling of each layer. This results in a laminated film with high smoothness.

[0078] A. Laminated film

[0079] The laminated film according to this embodiment has a transparent support substrate, an uncured hard coating layer formed on at least one surface of the transparent support substrate, and an uncured optical interference layer formed on the uncured hard coating layer. The uncured hard coating layer contains an active energy line curable hard coating forming composition. The uncured optical interference layer contains an active energy line curable optical interference layer forming composition.

[0080] Uncured refers to a state where the film is not fully cured. The hard coating and optical interference layer contained in a laminated film can be in a semi-cured state. Laminated films are post-cured.

[0081] Curing is synonymous with "curing and drying" as defined in JIS K 5500 (coating terminology). That is, curing means reaching the following state: a) when you try to firmly pinch the center of the test piece with your thumb and forefinger, no fingerprints are left on the coating surface, and you cannot feel the movement of the coating film. In addition, when you try to quickly and repeatedly rub the coating surface with your fingertips, no scratches are left (dry hard).

[0082] The cumulative light intensity was 200 mJ / cm 2 The laminated film with active energy lines can be said to be completely solidified.

[0083] Semi-curing is synonymous with "semi-cured drying" as defined in JIS K 5500 (coating terminology). That is, semi-curing refers to a state where, when you gently rub the center of the coating with your fingertip, no scratch is left (dry to touch). This is achieved after irradiation with a cumulative light intensity of 1 mJ / cm². 2 Above and below 200 mJ / cm 2 The laminated film with active energy lines can be considered semi-cured.

[0084] The hard coating and optical interference layer are not exposed to active energy lines, or are exposed to less than 1 mJ / cm. 2 The state after the active energy line can be described as uncured.

[0085] (Reflectivity)

[0086] The minimum reflectance R of the uncured optical interference layer side of a laminated film subjected to a heat treatment at 90°C for 30 minutes (hereinafter sometimes referred to as a specific heat treatment) is measured between wavelengths of 380 nm and 780 nm. AH Below 2.0%. Minimum reflectance R. AH Within this range, the generation of phase mixing between the uncured hard coating and the uncured optical interference layer is suppressed, and a clear interface is formed between the two layers. The minimum reflectivity R... AHPreferably, it is 1.8% or less, more preferably 1.6% or less. The minimum reflectance of the laminated film according to this embodiment can be 2.0% or less even after heat treatment at a temperature of 90°C or higher and 120°C or lower for 30 minutes or more and 90 minutes or less.

[0087] The laminated film involved in this embodiment has excellent anti-reflective properties. The molded body formed by curing it also has excellent anti-reflective properties. Utilizing the anti-reflective effect, external light entering the molded body can be reduced. The molded body has good display characteristics and good visibility.

[0088] Minimum reflectance R AH It is obtained by measuring all reflected light, including positively reflected light, in the wavelength region above 380 nm and below 780 nm. The minimum reflectance R... AH It is the minimum reflectance value among all wavelengths measured using the so-called SCI (Specular Component Include) method. Because this method is less affected by the surface condition of the object being measured, it can measure the reflectance of uncured layers.

[0089] Specifically, the minimum reflectance R of the laminated film AH It can be determined by the following methods.

[0090] Using a doctor blade coater, a black coating (e.g., trade name: CZ-805BLACK (manufactured by NIKKO BICSCo.,Ltd.) is applied to the side of the transparent support substrate opposite to the uncured hard coating, resulting in a dried film thickness of 3 μm or more and 6 μm or less. Then, the film is heat-treated at 90°C for 30 minutes to prepare evaluation sample M.

[0091] From the optical interference layer side of the obtained evaluation sample M, the reflectance in the wavelength region from 380 nm to 780 nm based on the SCI method is measured using a spectrophotometer (e.g., SD7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) at 10 nm wavelength intervals. The reflectance is measured at any 5 points or more (preferably 10 points) on the evaluation sample M. The minimum reflectance value is determined for each measurement point. The minimum reflectance R of the laminated film according to this embodiment is... AH The percentage did not exceed 2% at any of the measurement points.

[0092] Alternatively, a cumulative light intensity of 200 mJ / cm² can be used to irradiate the evaluation sample M. 2 The evaluation sample N, obtained from the above active energy lines, is used to measure the minimum reflectance R. AH This is because the reflectivity hardly changes before and after curing.

[0093] Ideally, the reflectivity should not change significantly before and after heat treatment. Therefore, it is not affected by deviations in production conditions during the process, and stable anti-reflection properties can be easily obtained. For example, the minimum reflectivity R... AH The minimum reflectance R measured on the uncured optical interference layer side of the laminated film before specific heat treatment. BH Preferred to satisfy 100×|R AH -R BH | / R BH The relationship is ≤20 (%). 100×|R AH -R BH | / R BH More preferably, it is 10% or less, and particularly preferably 5% or less.

[0094] According to the laminated film of this embodiment, low reflectivity can be maintained even when specific heat treatment is performed. Furthermore, the curing of the hard coating layer forming composition and the optical interference layer forming composition is almost negligible through the specific heat treatment. Therefore, specific heat treatment and additional heat treatment can be performed on the laminated film before complete curing without affecting reflectivity, adhesion, or elongation. The smoothness of each layer can be improved through heat treatment. Consequently, the smoothness of the resulting molded article is also improved.

[0095] The additional heat treatment conditions can be appropriately set according to the composition of each layer. The additional heat treatment temperature can be above 90℃ and below 220℃, above 100℃ and below 220℃, or above 110℃ and below 220℃. The additional heat treatment time can be above 10 seconds and below 10 minutes.

[0096] In the preforming process, the laminated film is thermoformed into the desired three-dimensional shape. Further heat treatment can be performed using the heat applied in the preforming process. By performing thermoforming at approximately 150°C to 190°C for 10 seconds to 5 minutes, preforming can be carried out while simultaneously allowing the uncured layers to fully level.

[0097] (Stretch rate)

[0098] Elongation of laminated film at 160℃ 160 The thickness is above 50%. In this case, the laminated film is fully stretched at a molding temperature above 150°C and below 190°C. This allows the laminated film to be molded into complex three-dimensional shapes without cracking. Damage to the laminated film is particularly easily suppressed during the preforming process. Therefore, molded bodies with complex three-dimensional shapes and the functions of both a hard coating layer and an optical interference layer can be obtained. The laminated film can be molded into three-dimensional shapes according to required physical properties and shapes, for example, through preforming and insert molding methods.

[0099] The functions of hard coatings and optical interference layers include, for example, excellent hard coating properties and anti-reflective properties. Examples of hard coating properties include, for instance, high hardness, wear resistance, and chemical resistance.

[0100] Elongation of laminated film 160 Preferably, it is 60% or more, more preferably 70% or more. The tensile strength E of the laminated film... 160 It can be less than 400%, less than 350%, or even less than 300%. The elongation of the molded body obtained by curing the laminated film at 160°C is less than 15%, and can be less than 5%.

[0101] Elongation E 160 For example, the following measurements can be taken.

[0102] Prepare a tensile testing machine with a clamp spacing of 150 mm and evaluation samples cut to 200 mm in length and 10 mm in width. Under conditions of 160°C, a tensile force of 5.0 kgf, and a tensile speed of 300 mm / min, stretch the evaluation samples by 10% along their long side. Visually inspect the stretched evaluation samples for cracks.

[0103] Without any cracks appearing, cut out a new sample and stretch it along its long side to 20%. Then, visually inspect for cracks. Repeat this process, increasing the stretching ratio by 10% each time, and record the stretching ratio at which the first crack is detected as the stretching ratio E of the laminate. 160 .

[0104] (thickness)

[0105] The thickness of the transparent support substrate is 50 μm or more and 600 μm or less. This allows the laminated film to maintain rigidity even when stretched. Furthermore, warping of the laminated film and the molded body is easily suppressed. In addition, since the transparent support substrate and the laminated film can be wound into rolls, roll-to-roll processing is possible.

[0106] The thickness of the transparent support substrate is preferably 100 μm or more, more preferably 200 μm or more. The thickness of the transparent support substrate is preferably 500 μm or less, more preferably 480 μm or less, further preferably 450 μm or less, and particularly preferably 400 μm or less.

[0107] There is no particular limitation on the thickness of the uncured hard coating. For example, the thickness of the uncured hard coating is 2 μm or more and 30 μm or less. An uncured hard coating refers to a hard coating that has dried but not yet cured (hereinafter referred to as an uncured hard coating). By having such a thickness, warping after curing is easily suppressed. In addition, hard coatings with excellent hard coating properties can be obtained.

[0108] The thickness of the uncured hard coating is more preferably 3 μm or more. The thickness of the uncured hard coating is more preferably 25 μm or less, and particularly preferably 20 μm or less.

[0109] The thickness of the uncured optical interference layer is not particularly limited. For example, the thickness of the uncured optical interference layer is 15 nm or more and 200 nm or less. Preferably, the thickness of the uncured optical interference layer is 60 nm or more, more preferably 65 nm or more. Preferably, the thickness of the uncured optical interference layer is 180 nm or less. If the thickness of the uncured optical interference layer is within this range, good anti-reflective properties can be imparted to the molded article.

[0110] (hardness)

[0111] From the perspective of easily suppressing damage in subsequent processes, the hardness H based on nanoindentation method is measured from the optical interference layer side of the laminated film. BC Preferably, it is 0.1 GPa or higher. If the hardness H BC If the pressure is above 0.1 GPa, it can suppress the formation of the cut and the depression or damage during cutting, as well as the depression, scraper marks or suction marks caused by foreign matter mixed in when multiple films are stacked, and easily improve the yield.

[0112] From the perspective of easily improving the adhesion between the uncured hard coating and the uncured optical interference layer, the hardness H BC Preferably, it should be below 0.5 GPa. If the hardness H BC When the hardness is below 0.5 GPa, the uncured optical interference layer is easily bonded to the uncured hard coating. Furthermore, when laminating the uncured hard coating and the uncured optical interference layer by bonding, air ingress into the interlayer (air trapping) can be suppressed. Specifically, the hardness H... BC Preferably, the hardness is above 0.1 GPa and below 0.5 GPa. Hardness H BC More preferably, it is 0.15 GPa or higher. Hardness H BC More preferably, it is below 0.4 GPa.

[0113] The cumulative light intensity was 2000 mJ / cm². 2 The hardness H of the laminated film with active energy lines (i.e., the cured laminated film (molded body)) measured by optical interference layer side based on nanoindentation method. AC Preferably, it is 0.25 GPa or higher. Hardness H AC Preferably, the hardness is below 0.7 GPa. Specifically, the hardness H AC Preferably, the hardness is above 0.25 GPa and below 0.7 GPa. After undergoing specific heat treatment, the hardness of the cured laminated film also meets the above range. Hardness H AC Preferably, it has a hardness of 0.3 GPa or higher. Hardness H ACIt can be below 0.6 GPa.

[0114] Hardness H of the molded body AC The hardness H of the laminated film BC Large. In this embodiment, at hardness H AC When the hardness H is above 0.25 GPa and below 0.7 GPa, BC It must meet the requirement of being above 0.1 GPa and below 0.5 GPa.

[0115] Hardness H BC and H AC The hardness H is calculated based on values ​​measured from the optical interference layer side of the laminated film or molded body using nanoindentation. BC and H AC The hardness H was measured under conditions where the surface condition of the optical interference layer and the hardness of the transparent support substrate had little impact. BC and H AC The hardness H is measured by pressing an indenter into the hard coating from the side of the optical interference layer. BC and H AC This reflects the hardness of the uncured or cured hard coating. For example, hardness H... BC and H AC The measurements were taken within 1000 nm of the surface of the optical interference layer.

[0116] Hardness based on nanoindentation is obtained using a nanoindentation device, for example, through continuous stiffness measurement. In continuous stiffness measurement, a quasi-static test load (DC load) and a small load (AC load) are applied to the sample. This causes the force applied to the sample to vibrate minutely. The stiffness relative to depth is calculated based on the vibrational component of the resulting displacement and the phase difference between the displacement and the load. Thus, a continuous distribution of hardness relative to depth can be obtained.

[0117] As a nanoindentation device, the iMicro Nanoindenter manufactured by NANOMECHANICS, INC. can be used. In continuous stiffness measurement methods, for example, the Advanced Dynamic E and H.NMT method can be used. Load and stiffness calculations can be performed using iMicro's dedicated software. A load is applied to the sample using the indenter up to a maximum load of 50 mN. For example, a Verkovich-type diamond indenter can be used as the indenter. When measuring and calculating stiffness, appropriate values ​​can be set for the Poisson's ratio and load of the object being measured (uncured hard coating and optical interference layer).

[0118] Hardness H was determined using nanoindentation method. BCSubsequently, if no indentation consistent with the shape of the indenter remains on the surface of the optical interference layer, the measured hardness H can be determined. BC Incorrect. The phenomenon described above is attributed to the uncured hard coating being too soft. That is, the measured hardness is not the hardness of the uncured hard coating, but rather strongly influenced by the transparent support substrate. Therefore, in the above situation, the hardness H... BC It can be considered to be below 0.1 GPa.

[0119] (Abrasion resistance)

[0120] From a visual perspective, the cured laminated film preferably exhibits excellent abrasion resistance. Preferably, it is produced after exposure to a cumulative light intensity of 2000 mJ / cm². 2 The surface of the optical interference layer of the stacked film with active energy lines is 4 cm on each side. 2 When a vertical load of 19.6 N is applied and rubbed for 3000 cycles, no visible scratches are observed in the optical interference layer. In this case, it is easy to suppress the decrease in visibility caused by changes in the appearance of the molded body. After undergoing specific heat treatment, the cured laminate also exhibits the above-mentioned wear resistance.

[0121] "Unvisual scratches" refer to scratches that cannot be observed visually. A scratch is, for example, surface roughness. If a scratch cannot be observed visually, it is acceptable to observe extremely small scratches when examining the sample after the wear test using a microscope with a magnification of 100x.

[0122] The wear test was conducted under the conditions described above using known methods. In the wear test, a friction element with a fixed piece of cotton cloth is typically used. A vertical load (specifically, every 4 cm) is applied to the sample through this friction element. 2 (19.6N).

[0123] The laminated film can undergo specific heat treatment before irradiation with the active energy line. Alternatively, or in lieu of specific heat treatment, the laminated film can be subjected to heat treatment for 30–60 seconds in an atmosphere at 150–190°C. Through these heat treatments, the surface of the laminated film is leveled, making it easier to further improve its wear resistance.

[0124] (Coefficient of static friction)

[0125] From the perspective of scratch resistance and abrasion resistance, a low static friction coefficient is preferred for cured laminated films. The cumulative light intensity was 2000 mJ / cm². 2 The static friction coefficient μ of the optical interference layer of the stacked film with active energy lines ACPreferably, the coefficient of static friction is 0.3 or less, more preferably 0.25 or less, and particularly preferably 0.20 or less. The static friction coefficient can be measured according to JIS K 7125. After undergoing specific heat treatment, the static friction coefficient of the cured laminated film also meets the above range.

[0126] The optical interference layer is laminated with an uncured hard coating layer in an uncured state. Furthermore, the laminated film is used for various processing in its uncured state. Therefore, in addition to anti-reflective properties, the optical interference layer is required to possess high hardness, low viscosity to prevent contamination, the ability to suppress damage and appearance changes during processing, and the ability to suppress curling caused by differences in thermal shrinkage compared to other layers. In particular, the optical interference layer requires excellent anti-reflective properties, low viscosity to prevent contamination, and the ability to suppress damage during processing (such as dents and scraper marks from suction marks in decorative processes).

[0127] These requirements can be achieved by controlling the hardness, rigidity, smoothness, and viscosity of the uncured optical interference layer. The aforementioned physical properties of the uncured optical interference layer can be adjusted by its thickness and the composition of the optical interference layer forming composition.

[0128] The hard coating is also laminated with the uncured optical interference layer in an uncured state. Furthermore, as described above, the laminated film is used for various processing in an uncured state. Therefore, the uncured hard coating, like the optical interference layer, is required to have high hardness, low viscosity to prevent contamination, the ability to suppress damage and appearance changes during processing (e.g., blistering and cracking in preforming processes), and the ability to suppress curling caused by differences in thermal shrinkage compared to other layers.

[0129] These requirements can be achieved by controlling the hardness, rigidity, smoothness, and tackiness of the uncured hard coating. The aforementioned physical properties of the uncured hard coating can be adjusted by its thickness and the composition of the hard coating forming composition.

[0130] The transparent support substrate and each layer of the laminated film of this embodiment will be further described below.

[0131] [Transparent Support Substrate]

[0132] There are no particular limitations on the transparency of the supporting substrate, as long as it is transparent. Specifically, transparency refers to a total light transmittance of 80% or more. The total light transmittance of the transparent supporting substrate is 80% or more, preferably 90% or more. The total light transmittance can be measured according to the method in JIS K7361-1. Materials known in the art can be used as the transparent supporting substrate without particular limitation. The transparent supporting substrate can be colorless or colored.

[0133] The transparent support substrate can be appropriately selected according to the application. Examples of transparent support substrates include polyester films such as polycarbonate (PC), polyethylene terephthalate, and polyethylene naphthalate; cellulose films such as diacetylcellulose and triacetylcellulose; 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 with cyclic or even norbornene structures, and ethylene-propylene copolymers; and amide films such as nylon and aromatic polyamides. Additionally, the transparent support substrate can be a film containing resins such as polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinyl butyral, polyacrylate, polyoxymethylene, and epoxy resin, or a film containing a mixture of these polymers.

[0134] The transparent support substrate can also be a laminate of multiple films. For example, the transparent support substrate can be a laminate of an acrylic resin film and a polycarbonate resin film.

[0135] Transparent support substrates can be optically anisotropic or isotropic. The magnitude of birefringence in anisotropic transparent support substrates is not particularly limited. The phase difference in anisotropic transparent support substrates can be either 1 / 4 (λ / 4) or 1 / 2 (λ / 2) of the wavelength.

[0136] [Uncured optical interference layer]

[0137] The uncured optical interference layer contains an active energy line-cured optical interference layer forming composition (hereinafter sometimes referred to as composition R). Composition R is cured by active energy lines. The hardness and / or elongation of the optical interference layer can be controlled by adjusting the cumulative light intensity of the active energy lines. The active energy lines are ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. Composition R is particularly preferably ultraviolet-cured.

[0138] The optical interference layer functions as a layer with a low refractive index. The refractive index of the cured optical interference layer is, for example, 1.20 or higher and 1.55 or lower, or 1.25 or higher and 1.50 or lower, or 1.30 or higher and 1.45 or lower. This provides good anti-reflective properties.

[0139] <<Optical Interference Layer Forming Composition>>

[0140] The optical interference layer forming composition (composition R) contains, for example, a first layer forming component and low-refractive-index particles. Low-refractive-index particles are particles with a low refractive index, which reduces the refractive index of the optical interference layer.

[0141] Low-refractive-index particles

[0142] Examples of low-refractive-index particles include hollow silica microparticles and hollow resin particles. Low-refractive-index particles can reduce the refractive index while maintaining the intensity of the optical interference layer. Low-refractive-index particles are structures filled with gas and / or porous structures containing gas. The refractive index decreases inversely with the gas occupancy. Therefore, low-refractive-index particles have a lower refractive index than particles that are not hollow.

[0143] As low-refractive-index particles, silica microparticles with a nanoporous structure formed in at least a portion of their interior and / or surface can be used. The nanoporous structure corresponds to the morphology, structure, aggregation state, and dispersion state of the silica microparticles within the coating film.

[0144] The volume average particle size (first-order particle size) of the low-refractive-index particles is preferably 50 nm or more and 200 nm or less. The thickness of the optical interference layer is designed taking into account the volume average particle size (first-order particle size) of the low-refractive-index particles. Specifically, the optical interference layer is designed to be thicker than the volume average particle size of the low-refractive-index particles. As a result, low-refractive-index particles are less likely to protrude from the surface of the optical interference layer, and the shedding of low-refractive-index particles from the optical interference layer when rubbing the surface of the optical interference layer is suppressed, which easily improves wear resistance.

[0145] Relative to 100 parts by mass of the solid component of composition R, the content of low-refractive-index particles is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more. This allows the optical interference layer to readily exhibit excellent anti-reflective properties. Relative to 100 parts by mass of the solid component of composition R, the content of low-refractive-index particles is preferably 80 parts by mass or less, more preferably 75 parts by mass or less, and particularly preferably 70 parts by mass or less.

[0146] <First Layer Formation Components>

[0147] The first layer forming component contains a first reactive component having two or more polymerizable functional groups per molecule. The first reactive component contains at least one selected from the first monomer, the first oligomer, and the first polymer. The weight-average molecular weight of the first monomer and the first oligomer is 10,000 or less, and may be 9,000 or less. The weight-average molecular weight of the first polymer exceeds 10,000, and may be 20,000 or more. The weight-average molecular weight of the first polymer may be 100,000 or less.

[0148] The weight-average molecular weight (Mw) can be calculated based on the molecular weight of standard polystyrene, using a chromatogram obtained by gel permeation chromatography.

[0149] From the viewpoint of adhesion and transparency to the uncured hard coating, the first reactive component preferably contains a (meth)acrylate compound. Examples of (meth)acrylate compounds include, for instance, acrylic (meth)acrylate monomers, acrylic (meth)acrylate oligomers, and acrylic (meth)acrylate polymers; urethane (meth)acrylate monomers, urethane (meth)acrylate oligomers, and urethane (meth)acrylate polymers; and silicone (meth)acrylate monomers, silicone (meth)acrylate oligomers, and silicone (meth)acrylate polymers. They can be used alone or in combination of two or more. "(meth)acrylate" refers to acrylates and / or methacrylates.

[0150] The acrylic equivalent of the first monomer and the first oligomer is not particularly limited. From a reactivity point of view, the acrylic equivalent of the first monomer and the first oligomer is preferably 100 g / eq. or more, more preferably 110 g / eq. or more, and particularly preferably 115 g / eq. or more. The acrylic equivalent of the first monomer and the first oligomer may be 200 g / eq. or less, 180 g / eq. or less, or 160 g / eq. or less.

[0151] Examples of (meth)acrylate monomers used as raw materials for (meth)acrylate compounds 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, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol acrylate, phenoxy polyethylene 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, dipentaerythritol hexaacrylate (DPHA), pentaerythritol (tri / tetra)acrylate (PETA), N-hydroxymethyl (meth)acrylamide, and N-hydroxy (meth)acrylamide.

[0152] As an oligomer or polymer of acrylic (meth)acrylate, polymers of at least one of the above-mentioned (meth)acrylate monomers can be listed as examples.

[0153] Carbamate (meth)acrylate monomers or oligomers can also be prepared, for example, by reacting polycarbonate diol, (meth)acrylate compounds containing hydroxyl and unsaturated double bond groups with polyisocyanates.

[0154] As a urethane (meth)acrylate polymer, at least one of the above-mentioned urethane (meth)acrylate monomers and oligomers can be listed as examples.

[0155] Silicone (meth)acrylate compounds are (meth)acrylate compounds containing siloxane bonds. While not limited to a specific theory for explanation, silicone (meth)acrylate compounds can be used to achieve low surface tension, improved leveling, and reduced viscosity in uncured optical interference layers.

[0156] From the perspective of improving wear resistance or stain resistance, and reducing refractive index, the first reactive component (representatively (meth)acrylate compounds) may also contain fluorine atoms. The first layer forming component may also contain non-reactive components with fewer than two polymerizable functional groups per molecule.

[0157] The miscibility is believed to be primarily caused by the thermal diffusion of small-molecule monomers and / or oligomers contained in the hard coating layer to the optical interference layer. Furthermore, low-refractive-index particles can suppress the thermal diffusion of monomers and / or oligomers from the hard coating layer to the optical interference layer. On the other hand, the first polymer has a limited effect on suppressing the thermal diffusion of monomers and / or oligomers from the hard coating layer to the optical interference layer.

[0158] From the viewpoint of suppressing miscibility, it is preferable to increase the proportion of low-refractive particles while decreasing the proportion of the first polymer. For example, in composition R, the first polymer is preferably contained in such a manner that the content X of low-refractive particles and the content Z of the first polymer satisfy the following relationship:

[0159] 100×Z / (X+Z)<40(%).

[0160] More preferably, the relationship satisfies 100×Z / (X+Z)≤35 (%). Particularly preferred is the relationship satisfying 100×Z / (X+Z)≤30 (%).

[0161] In particular, when the total content of low-refractive particles relative to the first oligomer, the first monomer, the first polymer, and the low-refractive particles is 30% or more by mass (X≥30), it is preferable that the content of low-refractive particles X, the total content of the first oligomer and the first monomer Y, and the content of the first polymer Z satisfy the following relationship:

[0162] X + Y + Z = 100,

[0163] Y≥0,

[0164] Z≥0, and

[0165] Z≤1 / 2X-15.

[0166] Therefore, it is easier to suppress miscibility. More preferably, the relationship Z ≤ 1 / 2X - 18 is satisfied, and particularly preferably, the relationship Z ≤ 1 / 2X - 20 is satisfied.

[0167] The effect of the first monomer and / or the first oligomer in suppressing miscibility is slightly less than that of the low-refractive particles, but it is important in improving various physical properties of the cured laminate (molded body).

[0168] <Inorganic oxide particles>

[0169] Composition R may contain inorganic oxide particles. By utilizing these inorganic oxide particles, rigidity can be easily improved while suppressing volume shrinkage of the uncured optical interference layer. Therefore, appearance changes during the manufacturing process of the uncured optical interference layer are easily suppressed. Furthermore, appearance changes and curling of the cured optical interference layer can also be suppressed. In addition, wear resistance is easily improved while reducing the tackiness of the cured optical interference layer.

[0170] The content of inorganic oxide particles is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more, relative to 100 parts by mass of the solid component of composition R. The content of inorganic oxide particles is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and particularly preferably 15 parts by mass or less, relative to 100 parts by mass of the solid component of composition R.

[0171] The solid component of composition R is all of its components except for the solvent. The same applies to the solid component of the hard coating composition.

[0172] The inorganic oxide particles are not particularly limited. Examples of inorganic oxide particles include silicon dioxide (SiO2) particles (excluding hollow particles), alumina particles, titanium dioxide particles, tin oxide particles, antimony-doped tin oxide (ATO) particles, and zinc oxide particles. The surface of the inorganic oxide particles can be modified with functional groups containing unsaturated double bonds. As a functional group, (meth)acryloyl group is preferred. Among these, from the viewpoint of cost and coating stability, silicon dioxide particles and alumina particles are preferred, and silicon dioxide particles and alumina particles with functional group modifications on their surfaces are particularly preferred. The inorganic oxide particles can be in the form of a sol.

[0173] The average particle size of inorganic oxide particles is not particularly limited. From the viewpoint of transparency and coating stability, the average particle size of inorganic oxide particles is preferably 5 nm or more and 100 nm or less. The average particle size of inorganic oxide particles is determined using image processing software based on cross-sectional images obtained using an electron microscope. The average particle size of other particulate matter can also be obtained using the same method.

[0174] Photopolymerization initiators

[0175] Composition R preferably contains a photopolymerization initiator. This facilitates the polymerization of the active energy line-curable resin component.

[0176] Examples of photopolymerization initiators include alkyl phenyl ketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanium ceramsite photopolymerization initiators, and oxime ester photopolymerization initiators.

[0177] Examples of alkyl phenyl ketone photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]phenyl}-2-methyl-propane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

[0178] Examples of acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0179] Examples of titanium decene-based photopolymerization initiators include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)-phenyl)titanium.

[0180] Examples of oxime ester polymerization initiators include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone 1-(O-acetyl oxime), oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, and 2-(2-hydroxyethoxy)ethyl ester. These photopolymerization initiators can be used alone or in combination of two or more.

[0181] Preferably, it is selected from at least one of 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone and 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0182] The content of the photopolymerization initiator relative to 100 parts by weight of the solid component of composition R is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, and particularly preferably 3 parts by weight or more. The content of the photopolymerization initiator relative to 100 parts by weight of the solid component of composition R is preferably 10 parts by weight or less, more preferably 7 parts by weight or less, and particularly preferably 5 parts by weight or less.

[0183] Solvent

[0184] Composition R may contain a solvent. The solvent is not particularly limited and can be appropriately selected considering the components contained in the composition, the type of transparent support substrate, and the coating method.

[0185] Examples of solvents 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 phenethyl ether; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosol solvents such as methyl cellosol, ethyl cellosol, and butyl cellosol; alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, and isobutanol; and halogen solvents such as dichloromethane and chloroform. These solvents can be used individually or in combination of two or more. Ester solvents, ether solvents, alcohol solvents, and ketone solvents are preferred.

[0186] <Other>

[0187] As needed, composition R may contain a variety of additives. Examples of additives include, for instance, antistatic agents, plasticizers, surfactants, antioxidants, UV absorbers, surface conditioners, surface modifiers, leveling agents, and light stabilizers (e.g., hindered amine light stabilizers (HALS)).

[0188] Relative to 100 parts by weight of the solid components of composition R, the content of each additive is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and particularly preferably 5 parts by weight or more. Relative to 100 parts by weight of the solid components of composition R, the content of each additive is preferably 20 parts by weight or less, more preferably 15 parts by weight or less.

[0189] [Uncured hard coating]

[0190] The uncured hard coating contains an active energy line curing type hard coating forming composition (hereinafter sometimes referred to as composition HC). Composition HC is cured by active energy lines. The hardness and / or elongation of the hard coating can be controlled by adjusting the cumulative light intensity of the active energy lines. Composition HC is preferably cured by the same type of active energy line as composition R.

[0191] <<Hard Coating Forming Compositions>>

[0192] The hard coating forming composition (composition HC) contains a second layer forming component.

[0193] <Second Layer Formation Components>

[0194] The second layer forming component contains a second reactive component having two or more polymerizable functional groups per molecule. The second reactive component preferably contains at least one of a second monomer and a second oligomer. This increases the crosslinking density of the second layer forming component, making it easier to increase the hardness of the cured hard coating. The weight-average molecular weight of the second monomer and the second oligomer is 10,000 or less, and can be 9,000 or less.

[0195] Relative to 100 parts by mass of the solid component of composition HC, the total content of the second oligomer and the second monomer is preferably 25 parts by mass or more and 65 parts by mass or less. If the total content of the second oligomer and the second monomer is 25 parts by mass or more relative to 100 parts by mass of the solid component of composition HC, it is easier to achieve a hardness H. BC The pressure is controlled to below 0.5 GPa. Therefore, the uncured hard coating layer and the uncured optical interference layer can easily adhere. Furthermore, when laminating the uncured hard coating layer and the uncured optical interference layer, it is easy to prevent air from entering the interlayer (air entrainment). The total content of the second oligomer and the second monomer is more preferably 28 parts by mass or more, and particularly preferably 30 parts by mass or more, relative to 100 parts by mass of the solid content of composition HC.

[0196] If the total content of the second oligomer and the second monomer is 65 parts by mass or less per 100 parts by mass of the solid component of composition HC, then the hardness H can be easily reduced. BC The pressure is controlled to be above 0.1 GPa. Therefore, it can suppress dents or damage during cut formation and trimming, dents caused by foreign matter mixed in when multiple laminated films are stacked, scraper marks, or suction marks, and easily improve the yield. The total content of the second oligomer and the second monomer is more preferably 62 parts by mass or less, particularly preferably 60 parts by mass or less, relative to 100 parts by mass of the solid component of composition HC.

[0197] From the viewpoint of suppressing the tackiness of uncured hard coatings, the second reactive component preferably contains a second polymer with a weight-average molecular weight exceeding 10,000, in addition to a second monomer and / or a second oligomer. The weight-average molecular weight of the second polymer exceeds 10,000, and can be 20,000 or more. Alternatively, the weight-average molecular weight of the second polymer can be less than 100,000.

[0198] As a preferred second reactive component, the same (meth)acrylate compounds exemplified as those exemplified as the first reactive component can be listed. From the viewpoint of adhesion or transparency to the transparent support substrate and the optical interference layer, the second reactive component preferably contains a (meth)acrylate compound.

[0199] <Inorganic oxide particles>

[0200] Composition HC may contain inorganic oxide particles. Substances exemplified in relation to composition R can be listed similarly as inorganic oxide particles. The content of inorganic oxide particles is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and particularly preferably 15 parts by mass or less, relative to 100 parts by mass of the solid content of composition HC. The content of inorganic oxide particles is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and particularly preferably 3 parts by mass or more, relative to 100 parts by mass of the solid content of composition HC.

[0201] Photopolymerization initiators

[0202] Composition HC preferably contains a photopolymerization initiator. This facilitates the polymerization of the active energy line curable resin component. Examples of photopolymerization initiators related to composition R can be listed similarly.

[0203] Preferably, it is selected from at least one of 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone and 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0204] The content of photopolymerization initiator is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the solid component of composition HC.

[0205] Solvent

[0206] Composition HC may contain a solvent. The solvent is not particularly limited and can be appropriately selected considering the components contained in the composition, the type of transparent support substrate, and the coating method. Similarly, substances exemplified in relation to composition R can be listed as solvents. Ester-based solvents, ether-based solvents, alcohol-based solvents, and ketone-based solvents are preferred.

[0207] <Other>

[0208] As needed, composition HC may contain various additives. Examples of additives exemplified in relation to composition R can also be listed.

[0209] The resin components of compositions HC and R can be the same or different. Preferably, the resin components of both are the same or identical. This is because the adhesion between the uncured hard coating and the uncured optical interference layer is improved, making interlayer delamination less likely.

[0210] [Uncured functional layer]

[0211] In a laminated film, at least one uncured functional layer may be present between the uncured hard coating layer and the uncured optical interference layer. This functional layer enhances the optical function of the laminated film or imparts new optical functions.

[0212] The functional layer can be another optical interference layer with different optical properties than the aforementioned optical interference layer. The functional layer can also be a combination of two or more other optical interference layers with different properties than the aforementioned optical interference layer.

[0213] Preferred functional layers are, for example, at least one of a high-refractive-index optical interference layer and a medium-refractive-index optical interference layer. The refractive index of the high-refractive-index layer can be greater than 1.55 and less than 2.00. The refractive index of the medium-refractive-index layer is not particularly limited, as long as it is between that of the optical interference layer (low-refractive-index layer) and the high-refractive-index layer. The refractive index of the medium-refractive-index layer can, for example, be greater than 1.55 and less than 1.75.

[0214] The thickness of the additional optical interference layers is not particularly limited. The thickness of each additional optical interference layer can be 10 nm or more and 300 nm or less. The thickness of each optical interference layer is preferably 15 nm or more, more preferably 20 nm or more, and particularly preferably 40 nm or more. The thickness of each optical interference layer is preferably 200 nm or less, more preferably 180 nm or less, and particularly preferably 150 nm or less.

[0215] The functional layer forming composition may contain the same components as those contained in the above-mentioned composition HC or composition R. The functional layer forming composition for forming additional optical interference layers may contain the same components as those contained in composition R. The functional layer forming composition for forming additional optical interference layers may contain high-refractive-index particles. The components contained in the multiple functional layers may be the same or different.

[0216] The high-refractive-index layer and the medium-refractive-index layer may contain resin components other than those that are cured by active energy lines. Other resin components may include, for example, thermoplastic resins such as alkyd resins, polyester resins, and acrylic resins; thermosetting resins such as epoxy resins, phenolic resins, melamine resins, urethane resins, and silicone resins; and polyisocyanates.

[0217] [Protective film]

[0218] In a laminated film, a protective film can be present on the side of the uncured optical interference layer opposite to the uncured hard coating layer. This makes it easier to suppress damage when the laminated film is wound into a roll or unwound from a roll.

[0219] The protective film not only protects the optical interference layer and the laminated films, but also functions as a release paper for molding composition R into a film. The protective film may have an adhesive layer on the coated surface.

[0220] Protective films known in the art can be used, without particular limitation. The protective film can be colorless or colored. The protective film can be transparent.

[0221] The thickness of the protective film is not particularly limited. The thickness of the protective film can be 20 μm or more and 100 μm or less. This easily improves the protective effect of the uncured optical interference layer. The thickness of the protective film is preferably 25 μm or more, more preferably 30 μm or more, further preferably 33 μm or more, and particularly preferably 35 μm or more. The thickness of the protective film is preferably 85 μm or less, more preferably 80 μm or less, and particularly preferably 65 μm or less. The thickness of the protective film is a value excluding the thickness of the adhesive layer.

[0222] Protective films are, for example, made of resin. Examples of resin films 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 to add further 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 and polyvinylidene chloride films, and polymethylpentene films.

[0223] Additives such as antistatic agents and UV protectants can be added to the resin film as needed. The surface of the resin film can be subjected to corona treatment or low-temperature plasma treatment.

[0224] Preferably, it is selected from at least one of polyethylene film, polystyrene film, modified polyolefin film, polymethylpentene film, OPP film and CPP film.

[0225] It is particularly preferred to select at least one of polyethylene film, polystyrene film, modified polyolefin film, polymethylpentene film, OPP film and CPP film with a thickness of 30 μm or more and 100 μm or less.

[0226] Figure 1 This is a schematic cross-sectional view of the laminated film according to this embodiment. The laminated film 10 includes a transparent support substrate 11, an uncured hard coating layer 12 disposed on one of its main surfaces, and an uncured optical interference layer 13 formed on the uncured hard coating layer 12.

[0227] B. Molded body

[0228] The molded body according to this embodiment is obtained by curing the above-described laminated film. The molded body is a fully cured product of the laminated film. The molded body has a transparent support substrate, a cured hard coating layer, and a cured optical interference layer. In the molded body, at least one cured functional layer may also be present between the cured hard coating layer and the cured optical interference layer. The molded body may also have a protective film, or may not have a protective film. The protective film is used depending on the intended use.

[0229] The molded body is formed by irradiating the laminated film, for example, with a cumulative light intensity of 200 mJ / cm. 2 The above active energy lines are used to cure the uncured hard coating and the uncured optical interference layer.

[0230] The molded material is particularly suitable as a protective material for displays and the various sensors configured around them. Examples of displays include liquid crystal displays, organic EL displays, and plasma displays. The molded material is especially suitable as a protective material for automotive touch panel displays and their surroundings. The molded material is configured with the optical interference layer positioned further out than the hard coating.

[0231] [Decorative Layer]

[0232] The molded body may also include a decorative layer. According to the laminated film of this embodiment, low reflectivity can be maintained even when heat treatment is performed during the formation of the decorative layer. When the molded body is a protective material for a display, the decorative layer may, for example, be provided on the bezel surrounding the display.

[0233] The molded body, for example, comprises a transparent support substrate, a hard coating and an optical interference layer disposed on one main surface of the transparent support substrate, and a decorative layer disposed on another main surface of the transparent support substrate. The decorative layer may be disposed on a portion of the other main surface of the transparent support substrate. The decorative layer is a layer that imparts decorations such as patterns, text, or metallic luster to the molded body. The decorative layer enhances the design flexibility of the molded body.

[0234] As a decorative layer, at least one of a printed layer and a vapor-deposited layer can be listed. There may be one or more printed layers and vapor-deposited layers, or multiple layers may be present. The thickness of the decorative layer is not particularly limited and can be appropriately set according to design considerations.

[0235] The printing layer may depict wood grain patterns, stone patterns, fabric patterns, sand patterns, geometric patterns, text, or cover the entire surface. The printing layer may be formed, for example, by a coloring ink containing a binder resin and a colorant. The binder resin is not particularly limited. Examples of binder resins include polyethylene resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl alcohol acetal resins, polyester urethane resins, cellulose ester resins, alkyd resins, and chlorinated polyolefin resins.

[0236] The colorant is not particularly limited, and well-known pigments or dyes can be listed. Examples of yellow pigments include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as titanium, nickel, and antimony oxides. Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as red lead. Examples of blue pigments include organic pigments such as phthalocyanine blue and 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.

[0237] The vapor-deposited layer is formed, for example, from at least one metal selected from aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, etc., or their alloys or compounds.

[0238] [Molded Resin Layer]

[0239] The molded body may also include a molding resin layer. The molding resin layer, together with a transparent support substrate, supports the hard coating and the optical interference layer. For example, the molded body may include a transparent support substrate, a hard coating and an optical interference layer disposed on one main surface of the transparent support substrate, and a molding resin layer disposed on another main surface of the transparent support substrate. The shape of the molding resin layer is not limited. Therefore, the design freedom of the molded body is increased.

[0240] The molded body may include a transparent support substrate, a hard coating and an optical interference layer disposed on one main surface of the transparent support substrate, a decorative layer disposed on another main surface of the transparent support substrate, and a molding resin layer. In this case, the decorative layer is disposed such that it is sandwiched between the transparent support substrate and the molding resin layer.

[0241] The resin forming the molding resin layer is not particularly limited. The molding resin layer may contain, for example, thermosetting resins and / or thermoplastic resins. Examples of thermosetting resins include phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyesters, and thermosetting polyimides. Examples of thermoplastic resins include so-called engineering plastics. Examples of engineering plastics include polyamides, polyacetals, polycarbonates, ultra-high molecular weight polyethylene, polysulfones, polyethersulfones, polyphenylene sulfide, and liquid crystal polymers.

[0242] Figure 2 This is a schematic cross-sectional view of the molded body according to this embodiment. The molded body 20 includes a transparent support substrate 11, a cured hard coating 22 disposed on one of its main surfaces, a cured light interference layer 23 formed on the hard coating 22, a decorative layer 24, and a molding resin layer 25. The decorative layer 24 is disposed such that it covers a portion of the other main surface of the transparent support substrate 11. The molding resin layer 25 is disposed such that it covers the entire other main surface of the transparent support substrate 11 and the entire decorative layer 24.

[0243] C. Manufacturing method of laminated films

[0244] The laminated film according to this embodiment is manufactured by a method comprising the following steps: a step of coating an active energy line curable hard coating forming composition on one side of a transparent support substrate with a thickness of 50 μm or more and 600 μm or less to form an uncured hard coating; a step of coating an active energy line curable optical interference layer forming composition on one side of another support substrate to form an uncured optical interference layer; and a lamination step of bonding the side of the uncured hard coating opposite to the transparent support substrate and the side of the uncured optical interference layer opposite to the other support substrate to obtain the laminated film. By using lamination to laminate the uncured hard coating and the uncured optical interference layer, phase miscibility is easily suppressed. The resulting laminated film has a tensile strength of 50% or more at 160°C, and the minimum reflectance R after specific heat treatment is [not specified]. AH It is below 2%.

[0245] Figure 3 This is a flowchart illustrating the method for manufacturing the laminated film according to this embodiment.

[0246] (1-1) Process for forming an uncured hard coating (S11)

[0247] There are no particular limitations on the method for forming an uncured hard coating. The uncured hard coating is formed by coating one side of a transparent support substrate, for example, with composition HC.

[0248] Composition HC can be prepared by methods commonly used by those skilled in the art. For example, it can be prepared by mixing the above components using a commonly used mixing device such as a paint shaker or mixer.

[0249] The coating method for composition HC is not particularly limited and can be carried out by methods commonly used by those skilled in the art. Examples of coating methods include dip coating, air knife coating, curtain coating, roller coating, doctor blade coating (e.g., wire rod coating), die coating, inkjet coating, and gravure coating.

[0250] There is no particular limitation on the coating amount of composition HC. Composition HC can be applied, for example, in a manner that results in a hard coating thickness of 2 μm or more but less than 30 μm after drying and uncuring.

[0251] After coating, a drying process can be performed. The drying conditions are not particularly limited, but are appropriately set to remove at least a portion of the solvent contained in the composition HC. Examples of drying methods include air drying (natural drying), heat drying, and vacuum drying. Heat drying is preferred. Heating allows the uncured hard coating to level out during drying. Drying is performed from the formation of the uncured hard coating on the transparent support substrate to the time the uncured hard coating is supplied to the lamination process. For example, the uncured hard coating is dried before the transparent support substrate with the uncured hard coating is fed into the lamination machine.

[0252] After the uncured hard coating is formed, the transparent support substrate can be wound into a roll. This allows for roll-to-roll processing before the lamination process. Furthermore, a protective film can be laminated onto the surface of the uncured hard coating before winding the transparent support substrate. The protective film and the uncured hard coating can be bonded together via an adhesive layer.

[0253] (1-2) Process for forming an uncured optical interference layer (S12)

[0254] There is no particular limitation on the method for forming the uncured optical interference layer. The uncured optical interference layer is formed, for example, by coating composition R onto one side of another supporting substrate (typically the aforementioned protective film). The coating method of composition R is the same as that of composition HC and can be performed by methods commonly used by those skilled in the art.

[0255] There is no particular limitation on the coating amount of composition R. Composition R is coated, for example, in a manner that results in an uncured optical interference layer thickness of 15 nm or more and 200 nm or less after drying.

[0256] After coating, a drying process can be performed. The drying conditions are not particularly limited, but should be appropriately set to remove at least a portion of the solvent contained in composition R. Methods similar to those used for drying hard coatings can be cited as drying methods. Heat drying is preferred. Heating allows the uncured optical interference layer to level out during drying.

[0257] Drying is performed between the formation of the uncured optical interference layer from another support substrate and the supply of the uncured optical interference layer to the lamination process. For example, the uncured optical interference layer is dried before the other support substrate with the uncured optical interference layer is fed into the lamination machine.

[0258] After the uncured optical interference layer is formed, another support substrate can be wound into a roll. This allows for roll-to-roll processing before the lamination process. Furthermore, a protective film can be laminated onto the surface of the uncured optical interference layer before winding the other support substrate. The protective film and the uncured optical interference layer can be bonded together via an adhesive layer.

[0259] (1-3) Lamination process (S13)

[0260] An uncured optical interference layer formed on a separate support substrate and an uncured hard coating formed on a transparent support substrate are laminated together. This yields a laminated film. After lamination, the separate support substrate can be peeled off.

[0261] In the case of winding another support substrate with an uncured optical interference layer, while feeding the transparent support substrate with an uncured hard coating into the laminator, the other wound support substrate is unwound and fed into the laminator.

[0262] In the case of a transparent support substrate with an uncured hard coating formed by winding, while feeding another support substrate with an uncured optical interference layer into the laminator, the already wound transparent support substrate is unwound and fed into the laminator.

[0263] The bonding is preferably performed while pressure is being applied. The pressure can be, for example, 0.1 N / cm or more and 50 N / cm or less. Preferably, the pressure is 0.5 N / cm or more. Preferably, the pressure is 30 N / cm or less.

[0264] There is no particular limitation on the temperature of each layer during lamination. Since each layer is uncured, lamination can be performed at low temperatures. On the other hand, since the laminated film involved in this embodiment easily suppresses the generation of miscible phases, each layer can be heated during lamination. The temperature of each layer during lamination can be above 0°C and below 100°C.

[0265] A laminated film having an uncured functional layer between an uncured hard coating layer and an uncured optical interference layer is manufactured, for example, by the following process.

[0266] First, another uncured functional layer is formed on the new support substrate. Next, the side of the uncured hard coating opposite to the transparent support substrate and the side of the uncured functional layer opposite to the new support substrate are bonded together. After peeling off the new support substrate, an uncured optical interference layer supported by another support substrate is bonded onto the exposed uncured functional layer. If necessary, the process of bonding the uncured functional layer to the uncured hard coating or the uncured functional layer stacked thereon is repeated before bonding the optical interference layer.

[0267] Thus, a laminated film is obtained comprising, in sequence, a transparent support substrate, an uncured hard coating, at least one uncured functional layer, an optical interference layer, and another support substrate. The other support substrate may or may not be peeled off. After the lamination process, the laminated film can be wound into a roll. In this case, the other support substrate is preferably not peeled off.

[0268] Figure 4 This is a schematic diagram illustrating the lamination process in the manufacturing method of the laminated film according to this embodiment. An uncured hard coating 12 is formed on one surface of the transparent support substrate 11. The laminate is obtained through the formation process of the uncured hard coating. The laminate is obtained from... Figure 4 It is transported from left to right in a flat manner.

[0269] On the other hand, an uncured optical interference layer 13 is laminated on one surface of another supporting substrate 14. This laminate is obtained through a process of forming the uncured optical interference layer. This laminate is derived from... Figure 4 It is transported from left to right in a flat manner.

[0270] While conveying these laminates, pressure is applied through a pair of rollers 30, thereby bonding the side of the uncured hard coating 12 opposite to the transparent support substrate 11 and the side of the uncured optical interference layer 13 opposite to the other support substrate 14. Thus, a laminated film is obtained which sequentially contains the transparent support substrate 11, the uncured hard coating 12, the optical interference layer 13, and the other support substrate 14.

[0271] The various dimensions in the illustrations are just one example. The thickness and size of each layer and substrate, as well as the position and size of the rollers, can be set appropriately.

[0272] D. Manufacturing method of molded body

[0273] The molded body according to this embodiment is manufactured, for example, by a method comprising the following steps: a decoration step of forming a decorative layer on another main surface of the transparent support substrate of the above-mentioned laminated film, and irradiating the laminated film with a cumulative light intensity of 200 mJ / cm after the decoration step. 2 The above describes the curing process of the active energy lines. The decoration process includes heating the laminated film at a temperature above 80°C for at least 20 minutes.

[0274] Following the decoration process, an injection molding process, or a preforming process followed by injection molding, may be performed as needed. In the preforming process, the laminated film is shaped into the desired three-dimensional form through thermoforming.

[0275] In the case of a preforming process, the curing process can be performed multiple times. For example, after the preforming process, a semi-curing process can be performed to cure a portion of the laminated film by irradiating it with active energy lines. In this case, after the injection molding process, a formal curing process is performed to cure the remaining portion of the laminated film by irradiating it with active energy lines.

[0276] That is, the molded body can be manufactured by, for example, by sequentially performing a decoration process (S21), a pre-forming process (S22), a curing process (S23), and an injection molding process (S24). Figure 5 This is a flowchart illustrating a method for manufacturing a molded body according to this embodiment.

[0277] The molded body can also be manufactured by, for example, by sequentially including a decoration process (S21), a pre-forming process (S22), a semi-curing process (S23-1), an injection molding process (S24), and a formal curing process (S23-2). Figure 6 This is a flowchart illustrating another method for manufacturing a molded body according to this embodiment.

[0278] When the laminated film is wound into a roll, before the decoration process, the laminated film can be unwound from the roll and cut into the desired shape and size.

[0279] The following is a description of each process.

[0280] (2-1) Decoration process (S21)

[0281] A decorative layer (typically a printed layer and a vapor-deposited layer) is formed on the other main surface of the transparent support substrate of the laminated film.

[0282] There are no particular limitations on the method for forming the printed layer. Examples of methods for forming the printed layer include offset printing, gravure printing, screen printing, roll coating, and spray coating. Similarly, there are no particular limitations on the method for forming the vapor-deposited layer. Examples of methods for forming the vapor-deposited layer include vacuum vapor deposition, sputtering, ion plating, and gold plating.

[0283] The decorative process includes heating the laminated film at 80°C or above for at least 20 minutes. This heating process is performed, for example, to dry the decorative layer. In this embodiment, even after undergoing such a heating process, the resulting molded article exhibits low reflectivity.

[0284] For example, the decorative process can be performed multiple times while changing the color. During the decorative process, further heating at temperatures exceeding 80°C for up to 5 minutes, or at temperatures below 80°C for more than 20 minutes, can also be performed. Such heating is not significantly related to the generation of miscible phases.

[0285] (2-2) Pre-forming process (S22)

[0286] The laminated film is pre-formed into a shape that closely resembles a three-dimensional form. Injection molding (typically insert molding lamination (IML)) is made possible by pre-shaping the laminated film into a shape close to a three-dimensional form. In IML molding, the laminated film is inserted into a mold, and molding resin is injected into the laminated film. After the pre-forming process, a trimming process can be performed to remove unwanted portions of the laminated film.

[0287] There are no particular limitations on the preforming method. Preforming can be performed, for example, by vacuum forming, air-forming, or vacuum-air-forming. In preforming, the mold and the laminated film are placed in the same processing chamber. The laminated film is positioned with the transparent support substrate facing the mold. The laminated film is heated, bringing the processing chamber to a vacuum and / or pressurized state. The laminated film is then deformed according to the mold. Next, the laminated film is cooled and removed from the mold. During preforming, the laminated film can be heated at 90°C or higher and 190°C or lower for 20 seconds to 5 minutes.

[0288] (2-3) Semi-curing process (S23-1)

[0289] Irradiation with active energy lines causes a portion of the laminated film to solidify, resulting in a semi-cured laminated film. This semi-curing process prevents the laminated film from adhering to the mold during injection molding and adjusts the film to the required elongation for injection molding, thereby suppressing crack formation during the injection molding process. The cumulative light intensity of the active energy lines is, for example, 1 mJ / cm². 2 Above and below 200 mJ / cm 2 After the semi-curing process, a finishing process can be performed to remove unwanted portions of the laminated film.

[0290] There is no particular limitation on the type of active energy rays. The active energy rays can be appropriately selected based on the type of resin component contained in the layer-forming composition. The active energy rays are not particularly limited and can be ionizing radiation rays such as ultraviolet light, electron beams, alpha rays, beta rays, and gamma rays. Ultraviolet light with a wavelength of 380 nm or less is preferred. Ultraviolet light can be irradiated using, for example, a high-pressure mercury lamp or an ultra-high-pressure mercury lamp.

[0291] (2-4) Injection molding process (S24)

[0292] In injection molding, for example, resin for molding is injected into a transparent support substrate while the light interference layer is facing the mold. Thus, while shaping the laminated film into the shape of the mold, a molding resin layer is formed on another main surface of the transparent support substrate.

[0293] (2-5) Curing process (S23), formal curing process (S23-2)

[0294] The laminated film is irradiated with active energy lines to completely cure it, thus obtaining the molded body. The cumulative light intensity of the active energy lines in the formal curing process is 200 mJ / cm². 2 The above. The cumulative light intensity of the active energy line can be 5000 mJ / cm. 2 The following can also be 3000mJ / cm 2 The active energy lines used in the semi-curing process can be the same as or different from those used in the semi-curing process.

[0295] The above method is just one example; well-known processing or manufacturing procedures can also be introduced as needed.

[0296] Example

[0297] The invention will be described in more detail through the following examples, but the invention is not limited thereto. In the examples, unless otherwise stated, "parts" and "%" are based on mass.

[0298] The components used in the examples and comparative examples are as follows.

[0299] (Polymer 1 and 2)

[0300] Acrylic polymer A: Mw70,000

[0301] Acrylic polymer B: Mw20,000

[0302] Acrylic polymer C: Mw 100,000

[0303] Acrylic polymers A, B, and C were prepared as follows.

[0304] [Preparation of acrylic polymer A]

[0305] A mixture consisting of 30.0 parts of 2,3-epoxypropyl methacrylate, 70 parts of methyl methacrylate, and 1.5 parts of tert-butyl 2-ethylhexanoate was prepared. Separately, 40.0 parts of toluene were added to a 500 ml reaction vessel equipped with a stirring blade, a nitrogen inlet tube, a cooling tube, and a dropping funnel, and the mixture was heated to 110°C. The mixture was added dropwise over a nitrogen atmosphere at a constant rate for 2 hours while stirring within the reaction vessel. After the addition was complete, the reaction was carried out at 110°C for 1 hour. Then, a mixed solution of 1.0 part of tert-butyl 2-ethylhexanoate and 25.0 parts of toluene was added dropwise to the reaction vessel over 1 hour. The reaction vessel was then heated to 145°C and the reaction was carried out for another 2 hours. The reaction vessel was then cooled to below 110°C, and 59.0 parts of toluene were added to obtain precursor A1.

[0306] 226.5 parts of precursor A1, 15.66 parts of acrylic acid, 0.43 parts of hydroquinone monomethyl ether, and 56 parts of toluene were separately placed into another reaction vessel of the same shape as described above, and heated to 90°C while stirring with air blowing. At 90°C, a mixed solution of 3.0 parts of toluene and 0.81 parts of tetrabutylammonium bromide was further added to the reaction vessel, and the reaction was carried out for 1 hour. Then, the temperature was raised to 105°C, and the reaction was carried out at 105°C until the acid value of the solid components in the reaction solution reached below 8. Next, a mixed solution of 0.43 parts of hydroquinone monomethyl ether and 3.0 parts of toluene was added to the above reaction solution, bringing the temperature to 75°C. Then, a mixed solution of 10.1 parts of KARENZ MOI (manufactured by Showa Denko), 5.0 parts of toluene, and 0.043 parts of dibutyltin dilaurate was added, and the reaction was carried out at 70°C for 2 hours. Then, the mixture was cooled to below 60°C, and a mixed solution of 2.0 parts methanol and 10.0 parts toluene was added. This yielded acrylic polymer A with a weight-average molecular weight of 70,000.

[0307] The acid value was determined according to JIS K5601-2-1, by titrating the above reaction solution with 0.1N potassium hydroxide (KOH) solution, and calculated using the following formula: Acid value = {(volume of KOH solution added [ml]) × (molar concentration of KOH solution [mol / L]} / (mass of solid component [g]). The same applies below.

[0308] [Preparation of Acrylic Polymer B]

[0309] A mixture consisting of 30.0 parts of 2,3-epoxypropyl methacrylate, 70 parts of methyl methacrylate, and 10.0 parts of tert-butyl 2-ethylhexanoate was prepared. Separately, 40.0 parts of toluene were added to a 500 ml reaction vessel equipped with a stirring blade, a nitrogen inlet tube, a cooling tube, and a dropping funnel, and the mixture was heated to 110°C. While stirring within the reaction vessel, the mixture was added dropwise at a constant rate over 2 hours under a nitrogen atmosphere. After the addition was complete, the reaction was carried out at 110°C for 1 hour. Then, a mixed solution of 1.0 part of tert-butyl 2-ethylhexanoate and 25.0 parts of toluene was added dropwise to the reaction vessel over 1 hour. The reaction vessel was then heated to 145°C and the reaction was carried out for another 2 hours. The reaction vessel was then cooled to below 110°C, and 59.0 parts of toluene were added to obtain precursor B1.

[0310] 306.5 parts of precursor B1, 15.66 parts of acrylic acid, 0.43 parts of hydroquinone monomethyl ether, and 56 parts of toluene were separately placed into another reaction vessel of the same shape as described above, and heated to 90°C while stirring with air blowing. At 90°C, a mixed solution of 3.0 parts of toluene and 0.81 parts of tetrabutylammonium bromide was further added to the reaction vessel, and the reaction was carried out for 1 hour. Then, the temperature was raised to 105°C, and the reaction was carried out at 105°C until the acid value of the solid components in the reaction solution reached below 8. Next, a mixed solution of 0.43 parts of hydroquinone monomethyl ether and 3.0 parts of toluene was added to the above reaction solution, bringing the temperature to 75°C. Then, a mixed solution of 10.1 parts of KARENZ MOI (manufactured by Showa Denko), 5.0 parts of toluene, and 0.043 parts of dibutyltin dilaurate was added, and the reaction was carried out at 70°C for 2 hours. Then, the mixture was cooled to below 60°C, and a mixed solution of 2.0 parts methanol and 10.0 parts toluene was added. This yielded acrylic polymer B with a weight-average molecular weight of 20,000.

[0311] [Preparation of acrylic polymer C]

[0312] A mixture consisting of 30.0 parts of 2,3-epoxypropyl methacrylate, 70 parts of methyl methacrylate, and 0.8 parts of tert-butyl 2-ethylhexanoate was prepared. Separately, 40.0 parts of toluene were added to a 500 ml reaction vessel equipped with a stirring blade, a nitrogen inlet tube, a cooling tube, and a dropping funnel, and the mixture was heated to 110°C. While stirring within the reaction vessel, the mixture was added dropwise at a constant rate over 2 hours under a nitrogen atmosphere. After the addition was complete, the reaction was carried out at 110°C for 1 hour. Then, a mixed solution of 1.0 part of tert-butyl 2-ethylhexanoate and 25.0 parts of toluene was added dropwise over 1 hour. The reaction vessel was then heated to 145°C and the reaction was continued for 2 hours. The reaction vessel was then cooled to below 110°C, and 59.0 parts of toluene were added to obtain precursor C1.

[0313] 295.8 parts of precursor C1, 15.66 parts of acrylic acid, 0.43 parts of hydroquinone monomethyl ether, and 56 parts of toluene were separately placed into another reaction vessel of the same shape as described above, and heated to 90°C while stirring with air blowing. At 90°C, a mixed solution of 3.0 parts of toluene and 0.81 parts of tetrabutylammonium bromide was further added to the reaction vessel, and the reaction was carried out for 1 hour. Then, the temperature was raised to 105°C, and the reaction was carried out at 105°C until the acid value of the solid components in the reaction solution reached below 8. Then, a mixed solution of 0.43 parts of hydroquinone monomethyl ether and 3.0 parts of toluene was added, bringing the temperature to 75°C. Next, a mixed solution of 10.1 parts of KARENZ MOI (manufactured by Showa Denko), 5.0 parts of toluene, and 0.043 parts of dibutyltin dilaurate was added, and the reaction was carried out at 70°C for 2 hours. Then, the mixture was cooled to below 60°C, and a mixed solution of 2.0 parts methanol and 10.0 parts toluene was added. This yielded acrylic polymer C with a weight-average molecular weight of 100,000.

[0314] (Oligomers 1 and 2 (polyfunctional urethane acrylate oligomers))

[0315] KRM-8452: Manufactured by Daicel-Allnex Ltd., Mw3,884, acrylic equivalent 120g / eq

[0316] CN-9893: Arkema KK Production

[0317] H-7M40: Manufactured by Genjo Industries, Mw10,000~15,000

[0318] UN-904M: Manufactured by Genjo Industries, Mw4,900

[0319] (Multifunctional acrylate oligomers)

[0320] ARONIX M-315: Manufactured by Dong-A Synthetic Co., Ltd., Mw450, acrylic equivalent 150g / eq

[0321] (Monomers 1 and 2 (polyfunctional acrylate monomers))

[0322] ARONIX M-402: Manufactured by Toa Synthetic Co., Ltd., DPHA

[0323] ARONIX M-305: Manufactured by Dong-A Synthetic Co., Ltd., PETA

[0324] (Low-refractive particles)

[0325] THRULYA 4320: Manufactured by Nippon Gas Chemical Co., Ltd., hollow silica microparticles with a volume average particle size of 55 nm.

[0326] THRULYA 5320: Manufactured by Nippon Gas Chemical Co., Ltd., hollow silica microparticles with a volume average particle size of 75nm.

[0327] (Inorganic oxide particles)

[0328] OSCAL 1842: Manufactured by Nichibukai Catalyst Chemical Industry Co., Ltd., reactive silica organosol, particle size 10nm

[0329] (Highly refractive particles)

[0330] NANON5 ZR-010: manufactured by SOLAR CO.,LTD., zirconium oxide, volume average particle size 20 nm

[0331] (Surface Conditioner)

[0332] OPTOOL: DAC-HP, made by DAIKIN INDUSTRIES, LTD.

[0333] (Surface modifier)

[0334] MEGAFACE RS-57: Made by DIC Corporation

[0335] (Photopolymerization initiator)

[0336] Omnirad 127: Manufactured by IGM Resins, α-hydroxyacetophenone

[0337] Omnirad 184: Manufactured by IGM Resins, α-hydroxyalkyl phenyl ketone

[0338] (Transparent support substrate)

[0339] TB1-TB5: Trade name AW-10U, manufactured by Wavelock Advanced Technology Co., Ltd., a double-layer (PMMA / PC) film composed of PMMA and PC, with thicknesses of 300μm (TB1), 200μm (TB2), 500μm (TB3), 30μm (TB4), and 100μm (TB5).

[0340] (Protective film)

[0341] Torayfan #40-2500, manufactured by Toray Industries, Inc., biaxially oriented polypropylene film (OPP), 40 μm thick.

[0342] [Preparation of composition LR1]

[0343] 3.1 parts of acrylic polymer B (first polymer), 27.7 parts of ARONIX M-402 (first monomer), 11.6 parts of OPTOOL DAC-HP (surface modifier), 8.0 parts of MEGAFACE RS-57 (surface modifier), and 3.5 parts of Omnirad 127 (photopolymerization initiator) were mixed. 46.1 parts of THRULYA 4320 (low refractive index particles) were further incorporated. This mixture was diluted with propylene glycol monomethyl ether to prepare a milky white composition LR1 with a solids concentration of 3%. The refractive index of the layer formed by composition LR1 is 1.20 or higher and 1.55 or lower.

[0344] [Preparation of composition LR2-LR15]

[0345] Except for the formulation shown in Table 1A, the same procedure was followed as with composition LR1 to prepare milky white compositions LR2-LR11, LR13-LR15, and transparent composition LR12 with a solid content concentration of 3%. The refractive index of the layers formed by compositions LR2-LR15 is 1.20 or higher and 1.55 or lower.

[0346] [Preparation of the functional layer forming composition HR1]

[0347] Except for the formulation shown in Table 1B, the same procedure as for composition LR1 was followed to prepare a milky white functional layer forming composition HR1 with a solid content concentration of 3%. The refractive index of the layer formed by composition HR1 is greater than 1.55 and less than 2.00.

[0348] [Preparation of Composition HC1]

[0349] 32.0 parts by weight of acrylic polymer A (second polymer), 36.3 parts by weight of KRM-8452 (second oligomer, a polyfunctional urethane acrylate oligomer), 21.3 parts by weight of ARONIX M-402 (second monomer), 4.1 parts by weight of OSCAL 1842 (inorganic oxide microparticles), and 6.3 parts by weight of Omnirad 184 (photopolymerization initiator) were mixed. The mixture was diluted with methyl isobutyl ketone to prepare a transparent composition HCl with a solids content of 35%.

[0350] [Preparation of Compositions HC2-HC5]

[0351] Except for the formulation shown in Table 1C, transparent compositions HC2 to HC5 with a solid content concentration of 35% were prepared by operating in the same manner as composition HC1.

[0352] [Example 1]

[0353] (1) Manufacturing of laminated films

[0354] (1-1) Formation of the uncured optical interference layer

[0355] The composition LR1 is coated onto an OPP film (protective film) using a gravure coating machine to achieve a dried thickness of 120 nm. Then, it is dried at 80°C for 1 minute to evaporate the solvent, forming an uncured optical interference layer. The protective film with the uncured optical interference layer is then wound into a roll.

[0356] Hereinafter, the optical interference layer formed by compositions LR1 to LR15 will sometimes be referred to as the "LR layer".

[0357] (1-2) Formation of uncured hard coating

[0358] The composition HC1 was applied to the PMMA surface of the transparent support substrate TB1 using a gravure coating machine to achieve a dried thickness of 12 μm. Then, it was dried at 80°C for 1 minute to allow the solvent to evaporate, forming an uncured hard coating.

[0359] Hereinafter, the hard coating formed by the compositions HC1 to HC5 will sometimes be referred to as the "HC layer".

[0360] (1-3) Stacking of uncured HC and LR layers

[0361] While unwinding the protective film, which is wound into a roll, the surfaces of the uncured HC layer supported by the transparent support substrate TB1 and the uncured LR layer supported by the protective film are bonded together. This produces a laminated film having, in sequence, the transparent support substrate, the uncured HC layer, the uncured LR layer, and the protective film. Finally, the laminated film is wound into a roll with the protective film facing inwards.

[0362] (2) Manufacturing of molded parts

[0363] (2-1) Formation of the decorative layer

[0364] First, the laminated film is unwound from the roll and cut into the desired shape and size. A decorative (printed) layer is then formed on the side of the cut laminated film opposite to the uncured HC layer on the transparent support substrate using screen printing, and dried at 80°C for 10 minutes. This decorative process is repeated 5 times, followed by drying at 90°C for 1 hour. Black ink (RIM Extreme Black, manufactured by JUJO CHEMICAL CO.,LTD.) is used in the formation of the printed layer.

[0365] (2-2) Peeling off the protective film

[0366] Next, the protective film is peeled off from the uncured LR layer at a speed of 5.0 mm / s.

[0367] (2-3) Preforming

[0368] The laminated film with the printing layer is heated at 190°C for 30 seconds, and pre-formed using a mold with a three-dimensional shape and a maximum depth of 6mm through vacuum compression molding.

[0369] (2-4) Curing

[0370] The cumulative light intensity of the preformed laminated film was 2000 mJ / cm. 2 The active energy lines. Next, adjustments are made.

[0371] (2-5) Injection molding

[0372] Finally, injection molding is performed to obtain a molded article having a molding resin layer (polycarbonate) on the printed layer side of the transparent support substrate. It should be noted that, in the embodiments, unless otherwise stated, ultraviolet light is used as the active energy line.

[0373] [evaluate]

[0374] The following evaluation was performed on the laminated films and molded articles. The results are shown in Table 2A.

[0375] (a) Thickness

[0376] Evaluation samples of 10 mm × 10 mm were cut from the laminated membrane. The cross-section of the evaluation sample was precipitated using a microtome (LEICA RM2265). The precipitated cross-section was observed using a laser microscope (VK8700, KEYENCE) or a transmission electron microscope (JEM2100, NEC). The thicknesses of 10 points each in the HC and LR layers were measured. The average values ​​were taken as the thicknesses of the HC and LR layers, respectively.

[0377] (b) Reflectivity

[0378] On the side of the transparent support substrate of the laminated film opposite to the uncured HC layer, a black coating (trade name: CZ-805BLACK (manufactured by NIKKOBICS Co., Ltd.) was applied using a doctor blade coater to achieve a dry film thickness of 3 μm or more but less than 6 μm. The laminated film coated with the black coating was then left to dry at room temperature for 5 hours to produce an uncured evaluation sample.

[0379] Reflectance was measured at 10 arbitrary points on the optical interference layer side of the evaluation sample using the SCI method. An SD7000 optical transducer (NDT) manufactured by Nippon Denshoku Kogyo Co., Ltd. was used for the measurements. Measurements were performed at 10 nm wavelength intervals within the wavelength range of 380 nm to 780 nm. The minimum reflectance was determined for each measurement point, and the largest of the 10 minimum values ​​was taken as the minimum reflectance R. BH .

[0380] The evaluation sample underwent a specific heat treatment, and the same procedure as described above was followed to determine the minimum reflectance R. AH .

[0381] (c) Elongation

[0382] Cut a test piece with a length of 200 mm and a width of 10 mm from the laminated film. Place the test piece on a tensile testing machine with a clamping distance of 150 mm, and stretch the evaluation sample by 10% along the long side under the conditions of 160°C, a tensile force of 5.0 kgf, and a tensile speed of 300 mm / min. Visually inspect the evaluation sample for cracks after stretching.

[0383] If no cracks are found, a new evaluation sample is cut out and then stretched by 20% along its long side. Then, the sample is visually inspected for cracks. This process is repeated while increasing the stretching ratio by 10% each time. The stretching ratio at which the first crack is detected is taken as the stretching ratio of the laminate. For evaluation samples cut from the same laminate, the above evaluation is performed three times, and the average stretching ratio obtained each time is taken as the stretching ratio E of the laminate. 160 .

[0384] (d) Coating hardness

[0385] Hardness H was measured from the uncured LR layer side of the laminated film and the LR layer side of the molded body, respectively. BC and hardness H AC .

[0386] Hardness was measured using an iMicro Nanoindenter manufactured by NANOMECHANICS, INC., via a continuous rigidity measurement method (method: Advanced Dynamic E and H.NMT).

[0387] Specifically, a small AC load is superimposed on the quasi-static test load and applied to the surface of the evaluation sample. The load is applied until the maximum load of 50 mN is reached. A Burkovich-type diamond indenter (with a tip curvature radius of 20 nm) is used as the indenter. Based on the vibrational components of the generated displacement and the phase difference between the displacement and the load, the continuous stiffness relative to depth is calculated to obtain the hardness distribution relative to depth. The hardness at a depth of 1000 nm in this distribution is then calculated.

[0388] iMicro's proprietary software was used for load and stiffness calculations. When calculating stiffness, the Poisson's ratio of the coating was set to 0.35. The load was controlled to ensure the strain rate... It reached 0.2.

[0389] (e) The reflection of external light

[0390] The light from the fluorescent lamp is reflected onto the surface of the light interference layer side of the molded body, and the reflection of external light is evaluated visually.

[0391] The evaluation criteria are as follows.

[0392] Good: Almost no external light is perceived.

[0393] Pass: Slightly detectable external light.

[0394] Poor: The intrusion of external light is clearly perceptible.

[0395] (f) Followability of three-dimensional shapes

[0396] Two molds with maximum depths of 3 mm and 6 mm were used to pre-form the laminated film and evaluate its ability to follow three-dimensional shapes.

[0397] The evaluation criteria are as follows.

[0398] Good: Even when molded into deep, three-dimensional shapes, no cracks or whitening were observed.

[0399] Acceptable: Cracks or whitening are visible when the shape is a deep, three-dimensional form.

[0400] However, cracks or whitening were not noticed when the shape was shallow and three-dimensional.

[0401] Defects: Cracks or whitening can be seen even when the shape is shallow and three-dimensional.

[0402] (g) Operability after preforming

[0403] The cumulative light intensity of the preformed laminated film was 2000 mJ / cm. 2 Evaluation samples were prepared using active energy lines. The operability of placing the evaluation samples in an injection molding mold was evaluated.

[0404] The evaluation criteria are as follows.

[0405] Good: The sample is evaluated as having toughness and can be easily set in an injection molding mold.

[0406] Acceptable: The sample exhibits weak toughness; although handling it presents some difficulties, it can be successfully placed in the mold.

[0407] Defect: The sample exhibits poor toughness and cannot be set in the mold.

[0408] (h) Warping of the molded body

[0409] An evaluation sample of 200 mm × 200 mm was cut from the laminated membrane and irradiated with a cumulative light intensity of 2000 mJ / cm². 2 The active energy line was then determined. Next, the evaluation sample was placed on a horizontal surface, and the amount of its four corners bulging from the horizontal surface (warpage) was measured using a ruler and averaged.

[0410] The evaluation criteria are as follows.

[0411] Optimal: Average warpage less than 10mm

[0412] Good: The average warpage is above 10 mm and below 15 mm.

[0413] Acceptable: The average warpage is 15mm or more and less than 20mm.

[0414] Defect: Average warpage exceeding 20mm

[0415] (i) Appearance after the finishing process

[0416] The laminated film after peeling off the protective film (2-2) and before preforming (2-3) is used as the evaluation sample. The evaluation sample is visually confirmed to have no scraping marks or suction marks caused by the decoration process.

[0417] The evaluation criteria are as follows.

[0418] Best: No scraping marks or suction marks

[0419] Good: Although there are a few scraper marks and suction marks, they disappear after heating to above 90°C and leveling out.

[0420] Acceptable: Although there are slight scraper marks and suction marks, they disappear after heating to above 150℃ and leveling out.

[0421] Defects: There are scraper marks and suction marks.

[0422] (j) Adhesion between the uncured HC layer and LR layer

[0423] The laminate of the protective film and the uncured optical interference layer prepared in (1-1) and the laminate of the transparent support substrate and the uncured hard coating prepared in (1-2) are pressed together by hand rollers with each layer facing each other, and the degree of adhesion is evaluated.

[0424] The evaluation criteria are as follows.

[0425] Good: The laminates adhere well to each other.

[0426] Acceptable: Although the laminates adhere to each other, the fit is weak.

[0427] (k) Pencil hardness

[0428] Evaluate the pencil hardness of the LR layer of the molded body.

[0429] The scratch hardness was determined according to JIS K5600-5-4 (1999) and the pencil method.

[0430] (l) Abrasion resistance

[0431] Apply a 4cm layer to the surface of the LR layer of the molded body. 2 The surface of the laminated film was subjected to a vertical load of 19.6 N and rubbed 3,000 times with a friction element secured with cotton cloth. The surface of the LR layer of the molded body was visually observed. The evaluation criteria are as follows.

[0432] Best: No visible scratches even after 3,000 rubs.

[0433] Good: Although no visible scratches were observed after 1,000 rubs, visible scratches were observed after 3,000 rubs.

[0434] Acceptable: After 1,000 rubs, no more than 5 visible scratches.

[0435] Defect: After 1,000 rubs, many visible scratches appear.

[0436] (m) Chemical resistance

[0437] A 10cm x 10cm evaluation sample was cut from the molded body. 2g of Neutrogena Sunscreen SPF45 (made by Johnson & Johnson KK) was applied evenly to the entire surface of the LR layer of the evaluation sample using a finger. Next, the sample was heated to 80°C for 4 hours. After cooling to room temperature, it was washed with water, and the appearance of the LR layer was visually evaluated.

[0438] The evaluation criteria are as follows.

[0439] Best: No external abnormalities

[0440] Good: While traces of coating are visible, lifting is not observed.

[0441] Defect: Causes bottom biting

[0442] [Examples 2-10, 12-22, Comparative Examples 3-10]

[0443] Using the compositions prepared according to the formulations shown in Tables 1A and 1C, laminated films and molded articles having the structures shown in Tables 2A to 2C were produced in the same manner as in Example 1. The resulting laminated films and molded articles were evaluated in the same manner as in Example 1. The results are shown in Tables 2A to 2C.

[0444] [Example 11]

[0445] The same procedure as in (1-1) and (1-2) of Example 1 was followed to form an uncured hard coating and an uncured optical interference layer, respectively.

[0446] In addition, the process is operated in the same manner as the formation step (1-1) of the uncured optical interference layer to obtain a protective film having an uncured functional layer (HR layer) with the composition shown in Table 1B. The protective film with the uncured HR layer formed is wound into a roll. While unwinding the protective film, the surface of the uncured HR layer supported by the protective film and the surface of the uncured HC layer supported by the transparent support substrate are bonded together.

[0447] Next, the protective film is peeled off to expose the uncured HR layer. The uncured LR layer prepared in (1-1) is then unwound and bonded to the HR layer. Thus, a laminated film and a molded article having uncured HC, HR, and LR layers sequentially are produced. The resulting laminated film and molded article are evaluated in the same manner as in Example 1. The results are shown in Tables 2A and 2B.

[0448] [Comparative Example 1]

[0449] Except for the use of composition HC4, the same procedure as in Example 1 was followed to form an uncured HC layer on the transparent support substrate TB1. The HC layer was then irradiated with a cumulative light intensity of 2000 mJ / cm². 2 The active energy lines cause the HC layer to solidify.

[0450] The composition LR11 was coated onto the cured HC layer. Next, the composition LR11 was dried to form an LR layer with a dry thickness of 120 nm. Finally, the layer was irradiated with a cumulative light intensity of 2000 mJ / cm². 2 The active energy lines were used to obtain a pre-cured laminated film. Using this laminated film, molded articles were fabricated and evaluated in the same manner as in Example 1. The results are shown in Table 2C.

[0451] [Comparative Example 2]

[0452] Except that composition LR1 was used instead of composition LR11, and composition HC5 was used instead of composition HC4, the procedure was the same as in Comparative Example 1 to obtain a pre-cured laminated film. Using this laminated film, molded articles were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2C.

[0453] [Table 1A]

[0454]

[0455] [Table 1B]

[0456]

[0457] [Table 1C]

[0458]

[0459]

[0460]

[0461]

[0462] As shown in Tables 2A and 2B, the laminated film according to this embodiment exhibits low reflectivity even after heat treatment. Furthermore, despite the high elongation (50% or more, specifically 70% or more) of the laminated film, the molded articles obtained from them possess excellent hard coating properties (e.g., high hardness, abrasion resistance, chemical resistance, etc.) and excellent anti-reflective properties. In addition, the laminated film according to this embodiment exhibits excellent conformability to molds with deep three-dimensional shapes during the preforming process.

[0463] The laminated films of Comparative Examples 1 and 2 are pre-cured. In Comparative Example 1, each layer is composed of a composition that can be stereolithographically molded to a certain extent after curing. As a result, the crosslinking density of the cured composition is low, resulting in poor abrasion resistance and chemical resistance. On the other hand, in Comparative Example 2, each layer is composed of a composition that has a high crosslinking density after curing, resulting in a product with excellent abrasion resistance and chemical resistance. Therefore, the laminated film of Comparative Example 2 lacks stereolithographic properties after curing, and even shallow three-dimensional shapes cannot be replicated in the pre-forming process.

[0464] The laminated film of Comparative Example 3, lacking an optical interference layer, exhibits a minimum reflectance exceeding 2%. The laminated films of Comparative Examples 4, 5, 8, and 9 show minimum reflectances exceeding 2% before and after specific heat treatments. Furthermore, in Comparative Examples 6 and 7, reflectance increases after specific heat treatments. In particular, while the minimum reflectance of the laminated film of Comparative Example 6 is small before the specific heat treatment, it significantly exceeds 2% afterward. In Comparative Example 10, the transparent support substrate is too thin, resulting in weak substrate rigidity and preventing the formation of a molded body.

[0465] Industrial availability

[0466] According to the present invention, a laminated film capable of being molded into complex three-dimensional shapes can be provided. Therefore, this laminated film is particularly preferred for use as a protective material in the manufacture of displays.

[0467] This application claims priority based on Japanese Patent Application No. 2020-202122 filed in Japan on December 4, 2020, the entire contents of which are incorporated herein by reference.

[0468] Symbol Explanation

[0469] 10-layer laminated film,

[0470] 11. Transparent support substrate

[0471] 12 Uncured hard coating,

[0472] 13 Uncured optical interference layer,

[0473] 14. Other supporting substrates,

[0474] 20 molded parts,

[0475] 22. Cured hard coating,

[0476] 23. Cured optical interference layer

[0477] 24 decorative layers,

[0478] 25. Molded resin layer,

[0479] 30 rollers.

Claims

1. A laminated membrane, which possesses: Transparent support substrate An uncured hard coating formed on at least one surface of the transparent support substrate, and An uncured optical interference layer is formed on the uncured hard coating. The uncured hard coating contains an active energy line curing type hard coating forming composition. The uncured optical interference layer contains an active energy line-cured optical interference layer forming composition. The thickness of the transparent support substrate is 50 μm or more and 600 μm or less. The laminated film has an elongation of more than 50% at 160°C. The minimum reflectance R of the laminated film after heat treatment at 90°C for 30 minutes, measured from the uncured optical interference layer side, between wavelengths of 380 nm and 780 nm. AH Less than 2%, The optical interference layer forming composition contains a first layer forming component and low-refractive particles. The first layer forming component contains a first reactive component having two or more polymerizable functional groups in one molecule. The first reactive component contains at least one selected from a first polymer with a weight average molecular weight greater than 10,000, a first oligomer with a weight average molecular weight less than 10,000, and a first monomer with a weight average molecular weight less than 10,000. The content X of the low-refractive particles, the total content Y of the first oligomer and the first monomer, and the content Z of the first polymer satisfy the following relationship: X + Y + Z = 100, X≥30， Y≥0， Z≥0， Z≤1 / 2X-15, and Excluding the case where Y and Z are both 0, The hard coating forming composition contains a second layer forming component. The second layer forming component contains a second reactive component having two or more polymerizable functional groups in one molecule. The second reactive component contains at least one of a second oligomer with a weight average molecular weight of less than 10,000 and a second monomer with a weight average molecular weight of less than 10,000. The total content of the second oligomer and the second monomer is 25 parts by mass or more and 65 parts by mass or less, relative to 100 parts by mass of the solids component of the hard coating forming composition. The thickness of the uncured optical interference layer is greater than 15 nm and less than 200 nm.

2. The laminated film according to claim 1, wherein, The minimum reflectance R AH The minimum value R of the reflectance of the laminated film before heat treatment, measured from the uncured optical interference layer side, between wavelengths of 380 nm and 780 nm. BH The following relationship must be satisfied: 100×|R AH -R BH | / R BH ≤20%。 3. The laminated film according to claim 1, wherein, The second reactive component also contains a second polymer with a weight-average molecular weight exceeding 10,000.

4. The laminated film according to claim 1 or 2, wherein, At least one uncured functional layer is also present between the uncured hard coating and the uncured optical interference layer.

5. The laminated film according to claim 1 or 2, wherein, The hardness H measured from the uncured optical interference layer side using nanoindentation method BC The range is above 0.1 GPa and below 0.5 GPa.

6. The laminated film according to claim 1 or 2, wherein, The cumulative light intensity was 2000 mJ / cm². 2 The hardness H of the optical interference layer side of the stacked film with active energy lines was measured by nanoindentation. AC The range is above 0.25 GPa and below 0.7 GPa.

7. The laminated film according to claim 1 or 2, wherein, The thickness of the uncured hard coating is greater than 2 μm and less than 30 μm.

8. Molded body, wherein, Contains a cured laminated film according to claim 1 or 2.

9. The molded article according to claim 8, wherein, The hard coating is disposed on one main surface of the transparent support substrate. The molded body also has a decorative layer disposed on another main surface of the transparent support substrate.

10. The molded body according to claim 9, further comprising a molding resin layer covering at least a portion of the decorative layer.

11. A method for manufacturing a laminated film, comprising: The process of forming an uncured hard coating by coating an active energy line curing type hard coating composition on one surface of a transparent support substrate with a thickness of 50 μm or more and 600 μm or less. The process of forming an uncured optical interference layer by coating an active energy line-curing optical interference layer onto one side of another supporting substrate, and A lamination process is performed by bonding the side of the uncured hard coating opposite to the transparent support substrate and the side of the uncured optical interference layer opposite to the other support substrate to obtain a laminated film. The laminated film has an elongation of more than 50% at 160°C. The minimum value R of the reflectance of the laminated film after heating at 90°C for 30 minutes, measured from the uncured optical interference layer side, between wavelengths of 380 nm and 780 nm. AH Less than 2%, The optical interference layer forming composition contains a first layer forming component and low-refractive particles. The first layer forming component contains a first reactive component having two or more polymerizable functional groups in one molecule. The first reactive component contains at least one selected from a first polymer with a weight average molecular weight greater than 10,000, a first oligomer with a weight average molecular weight less than 10,000, and a first monomer with a weight average molecular weight less than 10,000. The content X of the low-refractive particles, the total content Y of the first oligomer and the first monomer, and the content Z of the first polymer satisfy the following relationship: X + Y + Z = 100, X≥30， Y≥0， Z≥0， Z≤1 / 2X-15, and Excluding the case where Y and Z are both 0, The hard coating forming composition contains a second layer forming component. The second layer forming component contains a second reactive component having two or more polymerizable functional groups in one molecule. The second reactive component contains at least one of a second oligomer with a weight average molecular weight of less than 10,000 and a second monomer with a weight average molecular weight of less than 10,000. The total content of the second oligomer and the second monomer is 25 parts by mass or more and 65 parts by mass or less, relative to 100 parts by mass of the solids component of the hard coating forming composition. The thickness of the uncured optical interference layer is greater than 15 nm and less than 200 nm.

12. A method for manufacturing a molded body, comprising: The decorative process of forming a decorative layer on another main surface of the transparent support substrate of the laminated film according to claim 1 or 2, and A curing process that involves irradiating the laminated film with active energy lines after the decoration process; The decorative process includes a heating process of heating the laminated film at a temperature above 80°C for more than 20 minutes.

13. The method for manufacturing a molded article according to claim 12, wherein, After the decoration process, there is an injection molding process in which the light interference layer is oriented toward the mold and a resin for molding is injected into the decoration layer.

14. The method for manufacturing a molded article according to claim 13, wherein, The mold imparts a three-dimensional shape to the laminated film. After the decoration process and before the injection molding process, a pre-forming process is performed to shape the laminated film into a shape according to the three-dimensional shape.

Images