Optical film and image display device

Abstract

To provide an optical film having excellent scratch resistance, and an image display device including the same. [Solution] An optical film 10 is provided which comprises a light-transmitting substrate 11, a hard coat layer 12, and an inorganic layer 13 in this order, wherein the hard coat layer 12 is in contact with the inorganic layer 13, the hard coat layer 12 contains a binder resin 12A and inorganic particles 12B, the film thickness of the hard coat layer 12 is 1 μm or more, and the indentation hardness of the hard coat layer 12 is 200 MPa or more.

Description

REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority from an earlier Japanese application, Patent Application No. 2017-191319 (filing date: September 29, 2017), the entire disclosure of which is incorporated herein by reference. [Technical Field]

[0002] The present invention relates to an optical film and an image display device. [Background technology]

[0003] Optical films have been used in image display devices such as smartphones and tablet terminals. As the optical film, an optical film having a light-transmitting substrate, a hard coat layer, and an inorganic layer in this order may be used (for example, see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-128927 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in optical films having such inorganic layers, the surface of the inorganic layer is subjected to a 1 kg / cm scrubbing with #0000 steel wool. 2 When a steel wool test is performed in which the sample is rubbed back and forth 10 times while applying a load of 1000 kJ / cm, the inorganic layer may be scratched, or the inorganic layer may be scratched and the hard coat layer may be scraped off.

[0006] The present invention has been made to solve the above problems, and an object of the present invention is to provide an optical film having excellent scratch resistance and an image display device including the same. [Means for solving the problem]

[0007] The present invention includes the following inventions. [1] An optical film comprising a hard coat layer and an inorganic layer in this order, wherein the hard coat layer is in contact with the inorganic layer, the hard coat layer contains a binder resin and inorganic particles, the hard coat layer has a thickness of 1 μm or more, and the hard coat layer has an indentation hardness of 200 MPa or more.

[0008] [2] The optical film according to the above [1], wherein in a cross section of the hard coat layer in the thickness direction, the area ratio of the inorganic particles in a region from the interface between the hard coat layer and the inorganic layer to a depth of 500 nm in the hard coat layer is 5% or more and 75% or less.

[0009] [3] The optical film according to the above [1] or [2], wherein the inorganic particles are silica particles.

[0010] [4] An optical film comprising a light-transmitting substrate, a hard coat layer, and an inorganic layer in this order, wherein the hard coat layer is in contact with the inorganic layer, the hard coat layer contains at least one of a metal element and a semi-metal element, the hard coat layer has a thickness of 1 μm or more, and the hard coat layer has an indentation hardness of 200 MPa or more.

[0011] [5] The optical film according to any one of the above [1] to [4], wherein the inorganic layer is an inorganic oxide layer.

[0012] [6] The optical film according to any one of [1] to [4] above, wherein the inorganic layer contains silicon.

[0013] [7] The optical film according to any one of the above [1] to [6], wherein the inorganic layer has a thickness of 10 nm or more and 300 nm or less.

[0014] [8] The optical film according to any one of the above [4] to [7], wherein the hard coat layer contains a metalloid element, and the metalloid element is silicon.

[0015] [9] The optical film according to any one of [4] to [8] above, wherein the total atomic ratio of the metal element and the metalloid element contained in the hard coat layer, as measured by X-ray photoelectron spectroscopy, is 1.5% or more and 30% or less.

[0016]

[10] The optical film according to any one of the above [1] to [9], wherein the hard coat layer contains a polymer of a polymerizable compound containing silsesquioxane having a polymerizable functional group.

[0017]

[11] The optical film according to any one of [1] to

[10] above, which does not crack or break when a test of folding the optical film 180° so that the distance between opposing sides of the optical film is 6 mm is repeated 100,000 times.

[0018]

[12] The optical film according to any one of [1] to

[11] above, which does not crack or break when a test of folding the optical film 180° with the inorganic layer facing inward and with the distance between opposing sides of the optical film being 2 mm is repeated 100,000 times.

[0019]

[13] The optical film according to any one of the above [1] to

[12] , wherein the light-transmitting substrate is a substrate made of a polyimide resin, a polyamide resin, or a mixture thereof.

[0020]

[14] An image display device comprising: a display panel; and the optical film according to any one of [1] to

[13] above, which is disposed closer to a viewer than the display panel, wherein the hard coat layer of the optical film is located closer to the viewer than the light-transmitting substrate.

[0021]

[15] The image display device according to

[14] above, wherein the display panel is an organic light-emitting diode panel. [Effects of the Invention]

[0022] According to one aspect and another aspect of the present invention, an optical film having excellent scratch resistance can be provided, and according to another aspect of the present invention, an image display device including such an optical film can be provided. [Brief explanation of the drawings]

[0023] [Figure 1] 1 is a schematic diagram illustrating the configuration of an optical film according to a first embodiment. [Figure 2] FIG. 2 is an enlarged view of a portion of the optical film shown in FIG. [Figure 3] FIG. 10 is a diagram showing a folding test in a schematic manner. [Figure 4] 1 is a schematic configuration diagram of an image display device according to a first embodiment. [Figure 5] FIG. 4 is a schematic diagram illustrating the configuration of an optical film according to a second embodiment. [Figure 6] FIG. 10 is a schematic configuration diagram of an image display device according to a second embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0024] [First embodiment] An optical film and an image display device according to a first embodiment of the present invention will be described below with reference to the drawings. In this specification, terms such as "film" and "sheet" are not distinguished from each other solely based on the difference in name. Therefore, for example, "film" is used to include a member also called a sheet. FIG. 1 is a schematic diagram of the optical film according to this embodiment, FIG. 2 is an enlarged view of a portion of the optical film shown in FIG. 1, and FIG. 3 is a diagram schematically illustrating a folding test.

[0025] The optical film 10 shown in Fig. 1 includes a light-transmitting substrate 11, a hard coat layer 12, and an inorganic layer 13, in this order. The hard coat layer 12 is in contact with the inorganic layer 13. The optical film 10 further includes a functional layer 14 between the light-transmitting substrate 11 and the hard coat layer 12. Although the optical film 10 shown in Fig. 1 includes the functional layer 14, the optical film does not necessarily include the functional layer.

[0026] In Fig. 1, the surface 10A of the optical film 10 is the surface 13A of the inorganic layer 13. In this specification, the surface of the optical film is used to mean one surface of the optical film, and the surface opposite to the surface of the optical film is referred to as the back surface to distinguish it from the front surface of the optical film. The back surface 10B of the optical film 10 is the surface of the light-transmitting substrate 11 opposite to the surface on the hard coat layer 12 side.

[0027] The haze value (total haze value) of the optical film 10 is preferably 2.5% or less. If the haze value of the optical film 10 is 2.5% or less, excellent transparency can be obtained. The haze value is more preferably 1.5% or less, and more preferably 1.0% or less (the smaller the value, the more preferable).

[0028] The haze value can be measured using a haze meter (product name "HM-150" manufactured by Murakami Color Research Laboratory) according to JIS K7136:2000. After cutting out a 50 mm × 100 mm piece of optical film, the optical film is placed with the inorganic layer facing away from the light source, free of curls, wrinkles, fingerprints, dust, etc., and measured three times. The haze value is the arithmetic mean of the three measurements. In this specification, "measured three times" does not mean measuring the same location three times, but rather measuring three different locations. In the optical film 10, the surface 10A is flat when viewed with the naked eye, and the layers to be laminated, such as the hard coat layer 12, are also flat, and the film thickness variation is within a range of ±10%. Therefore, measuring the haze value at three different locations on the cut optical film is considered to provide an approximate average haze value for the entire in-plane of the optical film. The variation in haze value is within ±10%, even for measurement targets as long as 1 m x 3000 m or as small as a 5-inch smartphone. If the optical film cannot be cut to the above dimensions, for example, the HM-150 has a 20 mm diameter entrance opening for measurement, so a sample size of 21 mm or larger is required. Therefore, the optical film may be cut to a size of 22 mm x 22 mm or larger. For smaller optical films, measurement points are set to three by slightly shifting the measurement position or changing the angle within the range where the light source spot remains. When optical films are in roll form, they have an effective portion, which is the portion used in the product (e.g., an image display device), and an ineffective portion, which is the portion not used in the product. However, when cutting optical films for haze measurement, the effective portion of the optical film should be cut. For example, the portions of the optical film up to 5 cm from each end in the width direction may be ineffective portions.

[0029] Furthermore, if another film, such as a polarizing plate, is provided on one side of the optical film 10 via a pressure-sensitive adhesive layer or adhesive layer, the other film is peeled off together with the pressure-sensitive adhesive layer, and then the haze value of the optical film is determined. The peeling of the other film can be performed, for example, as follows: First, a laminate in which the other film is attached to the optical film via the pressure-sensitive adhesive layer or adhesive layer is heated with a dryer, and the blade of a cutter is inserted into the area believed to be the interface between the optical film and the other film, and the films are slowly peeled off. By repeating this heating and peeling process, the pressure-sensitive adhesive layer, adhesive layer, and other film can be peeled off. Incidentally, even if such a peeling process is performed, it does not significantly affect the haze value measurement.

[0030] The total light transmittance of the optical film 10 is preferably 80% or more. If the total light transmittance of the optical film 10 is 80% or more, sufficient light transparency can be obtained. The total light transmittance of the optical film 10 is more preferably 85% or more, and more preferably 90% or more (the larger the value, the more preferable).

[0031] The total light transmittance can be measured using a haze meter (product name "HM-150" manufactured by Murakami Color Research Laboratory) according to JIS K7361-1:1997. The optical film is cut into a size of 50 mm x 100 mm, and then placed with the inorganic layer facing away from the light source, free from curls, wrinkles, fingerprints, dust, etc., and measured three times. The arithmetic mean value of the three measurements is used for the total light transmittance. In the optical film 10, the visually observed surface 10A is flat, and the laminated layers, such as the hard coat layer 12, are also flat, with film thickness variations within a range of ±10%. Therefore, measuring the total light transmittance at three different points on the cut optical film is considered to provide an approximate average value for the total light transmittance of the entire in-plane optical film. The variation in total light transmittance is within ±10%, even when the measurement object is as long as 1m x 3000m, or the size of a 5-inch smartphone. If the optical film cannot be cut to the above size, it can be cut to an appropriate size of 22mm x 22mm or larger. If the optical film is small, three measurement points are used by shifting the light source spot slightly or by changing the angle, as long as the light source spot does not shift.

[0032] Furthermore, when another film such as a polarizing plate is provided on one side of the optical film 10 via a pressure-sensitive adhesive layer or an adhesive layer, the pressure-sensitive adhesive layer or the adhesive layer is peeled off together with the other film in the same manner as above, and then the total light transmittance of the optical film is measured. Note that even if such a peeling step is performed, it does not have a significant effect on the measurement of the total light transmittance.

[0033] The yellow index (YI) of the optical film 10 is preferably 15 or less. When the yellow index YI of the optical film 10 is 15 or less, the yellow tinge of the optical film is not noticeable, making it suitable for applications requiring transparency. The upper limit of the yellow index (YI) of the optical film 10 is more preferably 10 or less. The yellow index (YI) is calculated from the chromaticity tristimulus values ​​X, Y, and Z measured using a spectrophotometer (product name "UV-3100PC" manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp) on a 50 mm x 100 mm piece of optical film according to the formula specified in JIS Z8722:2009, and then calculated from the tristimulus values ​​X, Y, and Z according to the formula specified in ASTM D1925:1962. The yellow index (YI) is calculated by measuring one optical film three times and arithmetically averaging the values ​​obtained from the three measurements.

[0034] Furthermore, when another film such as a polarizing plate is provided on one side of the optical film 10 via a pressure-sensitive adhesive layer or an adhesive layer, the pressure-sensitive adhesive layer or the adhesive layer and the other film are peeled off together in the same manner as above, and then the yellow index (YI) is measured. Note that even if such a peeling step is performed, it does not have a significant effect on the measurement of the yellow index (YI).

[0035] In order to adjust the yellow index (YI) of the optical film 10, for example, a blue dye, which is a complementary color to yellow, may be contained in the light-transmitting substrate 11 or the hard coat layer 12. Even in cases where a substrate made of a polyimide resin is used as the light-transmitting substrate 11 and yellowing becomes a problem, the yellow index (YI) of the optical film 10 can be reduced by containing a blue dye in the light-transmitting substrate 11 or the hard coat layer 12.

[0036] The blue pigment may be either a pigment or a dye. However, for example, when the optical film 10 is used in an organic light-emitting diode display device, a pigment that combines light resistance and heat resistance is preferred. Polycyclic organic pigments and metal complex organic pigments, etc., are preferred as blue pigments for applications requiring light resistance, because they are less susceptible to molecular cleavage by ultraviolet light and have significantly better light resistance than molecularly dispersed dyes. More specifically, phthalocyanine organic pigments are preferred. However, because pigments are dispersed in solvents, particle scattering can impair transparency. Therefore, it is preferable to set the particle size of the pigment dispersion within the Rayleigh scattering region. On the other hand, when transparency of the optical film is important, it is preferable to use a dye that undergoes molecular dispersion in a solvent as the blue pigment.

[0037] The optical film 10 preferably has a transmittance of 8% or less for light with a wavelength of 380 nm. If the optical film has a transmittance of 8% or less, when the optical film is used in a mobile terminal, deterioration of the polarizer due to exposure to ultraviolet light can be suppressed. The upper limit of the transmittance of the optical film 10 is more preferably 5%. The transmittance can be measured using a spectrophotometer (product name "UV-3100PC", manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp). The transmittance is measured three times on an optical film cut into a size of 50 mm x 100 mm, and the arithmetic mean value of the three measurements is used. The transmittance of the optical film 10 can be achieved by, for example, adjusting the amount of ultraviolet absorber (described later) added to the hard coat layer 12.

[0038] From the viewpoint of foldability, the optical film 10 preferably does not crack or break even when the folding test described below is repeated 100,000 times, more preferably does not crack or break even when the folding test is repeated 200,000 times, and even more preferably does not crack or break even when the folding test is repeated 1,000,000 times. If cracks or the like occur in the optical film 10 when the folding test is repeated 100,000 times, the foldability of the optical film 10 is insufficient.

[0039] When another film such as a polarizing plate is provided on one side of the optical film via a pressure-sensitive adhesive layer or an adhesive layer, the folding test of the optical film is performed after peeling the other film together with the pressure-sensitive adhesive layer from the optical film by the same method as above. Furthermore, when a folding test is performed on a laminate in which the other film is attached to the optical film via a pressure-sensitive adhesive layer or an adhesive layer, it is preferable that the optical film does not crack or break even when the folding test is repeated 10,000 times.

[0040] The folding test is performed as follows. As shown in FIG. 3(A), in the folding test, first, side 10C of optical film 10 cut to a size of 20 mm x 100 mm and side 10D opposite side 10C are fixed by fixing parts 20 arranged in parallel. If the optical film cannot be cut to the above size, the optical film may be appropriately cut to a size of 20 mm x 40 mm or more. Furthermore, as shown in FIG. 3(A), fixing part 20 is slidable in the horizontal direction.

[0041] Next, as shown in Figure 3(B), the fixing portions 20 are moved closer to each other, thereby deforming the optical film 10 in a folding manner, and then, as shown in Figure 3(C), the fixing portions 20 are moved to a position where the distance between the two opposing side portions 10C, 10D of the optical film 10 fixed by the fixing portions 20 is 6 mm, and then the fixing portions 20 are moved in the opposite direction to eliminate the deformation of the optical film 10.

[0042] 3(A) to 3(C), the optical film 10 can be folded 180°. Furthermore, by performing a folding test so that the bent portion 10E of the optical film 10 does not protrude from the lower end of the fixed portion 20 and controlling the distance when the fixed portion 20 is closest using a spacer or the like, the distance between the two opposing sides of the optical film 10 can be set to 6 mm. In this case, the outer diameter of the bent portion 10E is considered to be 6 mm.

[0043] Furthermore, it is preferable that no cracks or breaks occur when a test in which the optical film 10 is folded 180° with the inorganic layer 13 on the inside and the distance between the opposing sides 10C and 10D of the optical film 10 is 2 mm is repeated 100,000 times. In this case, too, the folding test is performed in the same manner as above, except that the fixing part 20 of the optical film 10 is moved to a position where the distance between the two opposing sides 10C and 10D fixed by the fixing part 20 is 2 mm, and then the fixing part 20 is moved in the opposite direction to eliminate the deformation of the optical film 10, and then the folding test is performed.

[0044] Furthermore, when another film such as a polarizing plate is provided on one side of the optical film 10 via a pressure-sensitive adhesive layer or an adhesive layer, the pressure-sensitive adhesive layer or the adhesive layer and the other film are peeled off together in the same manner as above, and then the folding test is carried out. Note that even if such a peeling step is carried out, it does not have a significant effect on the folding test.

[0045] The surface 10A of the optical film 10 preferably has a hardness (pencil hardness) of 2H or greater when measured by the pencil hardness test specified in JIS K5600-5-4:1999. The pencil hardness test is performed on the surface of a 50 mm x 100 mm cut-out optical film using a pencil hardness tester (product name: "Pencil Scratch Coating Hardness Tester (Electric)" manufactured by Toyo Seiki Seisakusho Co., Ltd.) by applying a 750 g load to a pencil (product name: "Uni" manufactured by Mitsubishi Pencil Co., Ltd.) and moving the pencil at a speed of 1 mm / sec. The pencil hardness is defined as the highest hardness that does not scratch the surface of the optical film in the pencil hardness test. Pencil hardness is measured using multiple pencils of different hardness. Each pencil is tested five times. If the pencil hardness test does not scratch the surface of the optical film four or more times out of the five times, it is determined that the pencil of that hardness did not scratch the surface of the optical film. The scratches are visually observed when the surface of the optical film that has been subjected to the pencil hardness test is observed through transmission under fluorescent light. The pencil hardness of the surface 10A of the optical film 10 is more preferably 3H or more, even more preferably 5H, and most preferably 6H or more.

[0046] In recent years, light-emitting diodes (LEDs) have been widely adopted as backlight sources for image display devices such as personal computers and tablet terminals. However, these LEDs emit a strong light called blue light. This blue light has a wavelength of 380 to 495 nm and is similar to ultraviolet light. Because it has high energy, it is believed to reach the retina without being absorbed by the cornea or lens, causing retinal damage, eye fatigue, and adverse effects on sleep. Therefore, when applied to an image display device, an optical film is preferred that has excellent blue light blocking properties without affecting the color of the display screen. Therefore, from the perspective of blocking blue light, the optical film 10 preferably has a spectral transmittance of less than 1% at a wavelength of 380 nm, a spectral transmittance of less than 10% at a wavelength of 410 nm, and a spectral transmittance of 70% or more at a wavelength of 440 nm. If the spectral transmittance at a wavelength of 380 nm is 1% or more, or if the spectral transmittance at a wavelength of 410 nm is 10% or more, problems caused by blue light may not be resolved, while if the spectral transmittance at a wavelength of 440 nm is less than 70%, the color of the display screen of an image display device using the optical film may be affected. Optical film 10 sufficiently absorbs light in the wavelength range of 410 nm or less among blue light wavelengths, while sufficiently transmitting light with a wavelength of 440 nm or more, thereby achieving excellent blue light blocking without affecting the color of the display screen. Furthermore, when optical film 10 with such excellent blue light blocking properties is applied to an organic light-emitting diode (OLED) display device as an image display device, it is also effective in suppressing deterioration of the organic light-emitting diode elements.

[0047] The optical transmittance of the optical film 10 is preferably almost 0% up to a wavelength of 380 nm, gradually increases from a wavelength of 410 nm, and suddenly increases around 440 nm. Specifically, for example, the spectral transmittance preferably varies along a sigmoid curve between 410 nm and 440 nm. The spectral transmittance at 380 nm is more preferably less than 0.5%, even more preferably less than 0.2%; the spectral transmittance at 410 nm is more preferably less than 7%, even more preferably less than 5%; and the spectral transmittance at 440 nm is more preferably 75% or more, even more preferably 80% or more. The optical film 10 preferably has a spectral transmittance of less than 50% at a wavelength of 420 nm. By satisfying these spectral transmittance relationships, the optical film 10 exhibits a sudden increase in transmittance around 440 nm, achieving excellent blue light blocking properties without affecting the color of the display screen.

[0048] The optical film 10 more preferably has a spectral transmittance of less than 0.1% at a wavelength of 380 nm, a spectral transmittance of less than 7% at a wavelength of 410 nm, and a spectral transmittance of 80% or more at a wavelength of 440 nm.

[0049] The optical film 10 preferably has a transmission spectrum slope of greater than 2.0 in the wavelength range of 415 to 435 nm, obtained using the least-squares method. If the slope is less than 2.0, blue light wavelengths, such as those in the 415 to 435 nm wavelength range, may not be sufficiently blocked, resulting in a weak blue light blocking effect. It is also possible that the blue light wavelength range (415 to 435 nm) is blocked too much, which could result in interference with the backlight or emission wavelength range of an image display device (e.g., OLED emission at 430 nm), potentially resulting in poor color reproduction. The slope can be calculated, for example, by measuring transmittance data for at least five points between 415 and 435 nm, within a 1-nm range, using a spectrophotometer (product name "UV-3100PC" manufactured by Shimadzu Corporation) capable of measuring in 0.5-nm increments.

[0050] The optical film 10 preferably has a blue light blocking rate of 40% or more. If the blue light blocking rate is less than 40%, the problems caused by blue light described above may not be sufficiently resolved. The blue light blocking rate is, for example, a value calculated according to JIS T7333:2005. Note that such a blue light blocking rate can be achieved, for example, by making the hard coat layer 12 contain a sesamol-type benzotriazole-based monomer, which will be described later.

[0051] The use of the optical film 10 is not particularly limited, but examples of uses of the optical film 10 include image display devices such as smartphones, tablet terminals, personal computers (PCs), wearable terminals, digital signage, televisions, and car navigation systems. The optical film 10 is also suitable for in-vehicle use. The form of each of the above image display devices is also preferred for uses requiring flexibility, such as foldability and rollability.

[0052] The optical film 10 may be cut to a desired size or may be in a roll form. When the optical film 10 is cut to a desired size, the size of the optical film is not particularly limited and is appropriately determined depending on the size of the display surface of the image display device. Specifically, the size of the optical film 10 may be, for example, 2.8 inches to 500 inches. In this specification, "inches" refers to the length of the diagonal when the optical film is rectangular, the diameter when the optical film is circular, and the average value of the sum of the minor axis and the major axis when the optical film is elliptical. Here, when the optical film is rectangular, the aspect ratio of the optical film used to calculate the above-mentioned inches is not particularly limited as long as it does not cause any problems as a display screen for the image display device. Examples include length:width = 1:1, 4:3, 16:10, 16:9, and 2:1. However, these aspect ratios are not limited, particularly for in-vehicle applications and digital signage, which require sophisticated design. Furthermore, if the optical film 10 is large, it is cut out from an arbitrary position to an A5 size (148 mm×210 mm), and then cut out to the size of each measurement item.

[0053] The optical film 10 may be disposed inside the image display device, but is preferably disposed near the surface of the image display device. When used near the surface of the image display device, the optical film 10 functions as a cover film used in place of a cover glass.

[0054] <<Light transparent base material>> The light-transmitting substrate 11 is a substrate that has light transparency. In this specification, "light transparency" means the property of transmitting light, and includes, for example, a total light transmittance of 50% or more, preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more. Light transparency does not necessarily mean transparency, and may also be translucent.

[0055] The thickness of the light-transmitting substrate 11 is preferably 10 μm or more and 100 μm or less. A light-transmitting substrate having a thickness of 10 μm or more can suppress curling of the optical film 10, and also provides sufficient hardness, enabling a pencil hardness of 3H or more. Furthermore, when the optical film is manufactured by a roll-to-roll method, wrinkles can be suppressed, which reduces the risk of deterioration in appearance. On the other hand, a light-transmitting substrate 11 having a thickness of 100 μm or less provides sufficient folding performance for the optical film and is also preferable in terms of weight reduction. The thickness of the light-transmitting substrate is determined by photographing a cross section of the light-transmitting substrate using a scanning electron microscope (SEM), measuring the thickness of the light-transmitting substrate at 10 points on the image of the cross section, and calculating the arithmetic mean value of the thicknesses at the 10 points. The lower limit of the light-transmitting substrate 11 is more preferably 25 μm or more, and the upper limit of the light-transmitting substrate 11 is more preferably 80 μm or less.

[0056] Examples of materials constituting the light-transmitting substrate 11 include resins such as polyimide resins, polyamideimide resins, polyamide resins, and polyester resins (e.g., polyethylene terephthalate and polyethylene naphthalate). Among these, polyimide resins, polyamide resins, or mixtures thereof are preferred, as they are not only less likely to crack or break in a folding test, but also have excellent hardness and transparency, are excellent in heat resistance, and can be imparted with even greater hardness and transparency by baking.

[0057] The polyimide resin is obtained by reacting a tetracarboxylic acid component with a diamine component. The polyimide resin is not particularly limited, but it is preferable that the polyimide resin has at least one structure selected from the group consisting of structures represented by the following general formula (1) and the following general formula (3), in terms of excellent light transmittance and excellent rigidity.

[0058] [ka]

[0059] In the above general formula (1), R1 is a tetravalent group which is a tetracarboxylic acid residue, R 2 represents at least one divalent group selected from the group consisting of trans-cyclohexanediamine residue, trans-1,4-bismethylenecyclohexanediamine residue, 4,4'-diaminodiphenylsulfone residue, 3,4'-diaminodiphenylsulfone residue, and a divalent group represented by the following general formula (2): n represents the number of repeating units and is 1 or more. In this specification, "tetracarboxylic acid residue" refers to a residue obtained by removing four carboxyl groups from a tetracarboxylic acid, and represents the same structure as the residue obtained by removing the acid dianhydride structure from a tetracarboxylic acid dianhydride. Furthermore, "diamine residue" refers to a residue obtained by removing two amino groups from a diamine.

[0060] [ka] In the above general formula (2), R 3 and R 4 each independently represents a hydrogen atom, an alkyl group, or a perfluoroalkyl group.

[0061] [ka]

[0062] In the above general formula (3), R 5 represents at least one tetravalent group selected from the group consisting of a cyclohexanetetracarboxylic acid residue, a cyclopentanetetracarboxylic acid residue, a dicyclohexane-3,4,3',4'-tetracarboxylic acid residue, and a 4,4'-(hexafluoroisopropylidene)diphthalic acid residue; R 6 represents a divalent group that is a diamine residue, and n' represents the number of repeating units and is 1 or more.

[0063] In the above general formula (1), R 1 is a tetracarboxylic acid residue, and can be a residue obtained by removing the acid dianhydride structure from the tetracarboxylic acid dianhydride listed above. 1Among these, from the viewpoint of improving light transmittance and improving rigidity, it is preferable that the dicarboxylic acid ester contains at least one selected from the group consisting of 4,4'-(hexafluoroisopropylidene)diphthalic acid residue, 3,3',4,4'-biphenyltetracarboxylic acid residue, pyromellitic acid residue, 2,3',3,4'-biphenyltetracarboxylic acid residue, 3,3',4,4'-benzophenonetetracarboxylic acid residue, 3,3',4,4'-diphenylsulfonetetracarboxylic acid residue, 4,4'-oxydiphthalic acid residue, cyclohexanetetracarboxylic acid residue, and cyclopentanetetracarboxylic acid residue, and it is further preferable that the dicarboxylic acid ester contains at least one selected from the group consisting of 4,4'-(hexafluoroisopropylidene)diphthalic acid residue, 4,4'-oxydiphthalic acid residue, and 3,3',4,4'-diphenylsulfonetetracarboxylic acid residue.

[0064] R 1 In the present invention, the total content of these suitable residues is preferably 50 mol % or more, more preferably 70 mol % or more, and even more preferably 90 mol % or more.

[0065] Also, R 1 It is also preferable to use a mixture of a group of tetracarboxylic acid residues (Group A) suitable for improving rigidity, such as at least one selected from the group consisting of 3,3',4,4'-biphenyltetracarboxylic acid residues, 3,3',4,4'-benzophenonetetracarboxylic acid residues, and pyromellitic acid residues, and a group of tetracarboxylic acid residues (Group B) suitable for improving transparency, such as at least one selected from the group consisting of 4,4'-(hexafluoroisopropylidene)diphthalic acid residues, 2,3',3,4'-biphenyltetracarboxylic acid residues, 3,3',4,4'-diphenylsulfonetetracarboxylic acid residues, 4,4'-oxydiphthalic acid residues, cyclohexanetetracarboxylic acid residues, and cyclopentanetetracarboxylic acid residues.

[0066] In this case, the content ratio of the tetracarboxylic acid residue group (Group A) suitable for improving rigidity to the tetracarboxylic acid residue group (Group B) suitable for improving transparency is preferably 0.05 mol or more and 9 mol or less, more preferably 0.1 mol or more and 5 mol or less, and even more preferably 0.3 mol or more and 4 mol or less, of the tetracarboxylic acid residue group (Group A) suitable for improving rigidity per 1 mol of the tetracarboxylic acid residue group (Group B) suitable for improving transparency.

[0067] R in the above general formula (1) 2 Among these, from the viewpoints of improving light transmittance and improving rigidity, R3 is preferably at least one divalent group selected from the group consisting of a 4,4'-diaminodiphenylsulfone residue, a 3,4'-diaminodiphenylsulfone residue, and a divalent group represented by the above general formula (2), and more preferably at least one divalent group selected from the group consisting of a 4,4'-diaminodiphenylsulfone residue, a 3,4'-diaminodiphenylsulfone residue, and a divalent group represented by the above general formula (2) in which R3 and R4 are perfluoroalkyl groups.

[0068] R in the above general formula (3) 5 Among these, from the viewpoint of improving light transmittance and rigidity, it is preferable that the diphthalic acid group contains a 4,4'-(hexafluoroisopropylidene)diphthalic acid residue, a 3,3',4,4'-diphenylsulfonetetracarboxylic acid residue, and an oxydiphthalic acid residue.

[0069] R 5 In the formula (I), these suitable residues are preferably contained in an amount of 50 mol % or more, more preferably 70 mol % or more, and even more preferably 90 mol % or more.

[0070] R in the above general formula (3) 6is a diamine residue, and can be a residue obtained by removing two amino groups from the diamines exemplified above. R6 in the general formula (3) above is, among others, a 2,2'-bis(trifluoromethyl)benzidine residue, a bis[4-(4-aminophenoxy)phenyl]sulfone residue, a 4,4'-diaminodiphenylsulfone residue, a 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane residue, a bis[4-(3-aminophenoxy)phenyl]sulfone residue, a 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl ether residue, a 1,4-bis[4-amino-2-(trifluoromethyl)phenoxy]benzene residue, a 2,2-bis[4-(4-amino-2-trifluoromethyl ...trifluoromethyl)phenoxy]benzene residue, a 2,2-bis[4-(4-amino-2-trifluoromethyl)phenyl]sulfone residue, a 2,2-bis[4-(4-amino-2-trifluoromethyl)phenyl]sulfone residue, a 2,2-bis[4-(4-amino-2-trifluoromethyl)phenyl]sulfone residue, a 2,2-bis[4-(4-amino-2-trifluoromethyl)phenyl]sulfone residue, a 2,2-bis[4-(4-amino-2-trifluoromethyl)phenyl]sulfone residue, a 2,2-bis[4-(4-amino-2- It is preferable that the 4,4'-diamino-2-(trifluoromethylphenoxy)phenyl]hexafluoropropane residue, 4,4'-diamino-2-(trifluoromethyl)diphenyl ether residue, 4,4'-diaminobenzanilide residue, N,N'-bis(4-aminophenyl)terephthalamide residue, and 9,9-bis(4-aminophenyl)fluorene residue, and it is further ... 4,4'-diamino-2-(trifluoromethylphenoxy)phenyl]hexafluoropropane residue, 4,4'-diamino-2-(trifluoromethyl)diphenyl ether residue, 4,4'-diaminobenzanilide residue, 4,4'-diamino-2-(trifluoromethylphenoxy)phenyl]hexafluoropropane residue, 4,4'-diamino-2-(trifluoromethyl)diphenyl ether residue, 4,4'-diaminobenzanilide residue, 4

[0071] R 6 In the present invention, the total content of these suitable residues is preferably 50 mol % or more, more preferably 70 mol % or more, and even more preferably 90 mol % or more.

[0072] Also, R 6and a diamine residue group (Group C) suitable for improving rigidity, such as at least one selected from the group consisting of bis[4-(4-aminophenoxy)phenyl]sulfone residue, 4,4'-diaminobenzanilide residue, N,N'-bis(4-aminophenyl)terephthalamide residue, paraphenylenediamine residue, metaphenylenediamine residue, and 4,4'-diaminodiphenylmethane residue; and a diamine residue group (Group C) suitable for improving rigidity, such as at least one selected from the group consisting of 2,2'-bis(trifluoromethyl)benzidine residue, 4,4'-diaminodiphenylsulfone residue, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane residue, bis[4-(3-aminophenoxy)phenyl]sulfone residue, It is also preferred to use a mixture of the diamine residues with at least one diamine residue group (Group D) suitable for improving transparency, such as at least one selected from the group consisting of 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl ether residue, 1,4-bis[4-amino-2-(trifluoromethyl)phenoxy]phenyl]sulfone residue, 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl ether residue, 1,4-bis[4-amino-2-(trifluoromethyl)phenoxy]benzene residue, 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane residue, 4,4'-diamino-2-(trifluoromethyl)diphenyl ether residue, and 9,9-bis(4-aminophenyl)fluorene residue.

[0073] In this case, the content ratio of the diamine residue group suitable for improving rigidity (Group C) to the diamine residue group suitable for improving transparency (Group D) is preferably 0.05 to 9 moles, more preferably 0.1 to 5 moles, and even more preferably 0.3 to 4 moles, of the diamine residue group suitable for improving rigidity (Group C) per 1 mole of the diamine residue group suitable for improving transparency (Group D).

[0074] In the structures represented by the general formula (1) and the general formula (3), n and n' each independently represent the number of repeating units and are 1 or more. The number of repeating units n in the polyimide is not particularly limited and may be appropriately selected depending on the structure so as to exhibit a preferred glass transition temperature, which will be described later. The average number of repeating units is usually 10 to 2,000, and preferably 15 to 1,000.

[0075] The polyimide resin may also contain a polyamide structure in part thereof, such as a polyamideimide structure containing a tricarboxylic acid residue such as trimellitic anhydride, or a polyamide structure containing a dicarboxylic acid residue such as terephthalic acid.

[0076] From the viewpoint of heat resistance, the polyimide resin preferably has a glass transition temperature of 250° C. or higher, more preferably 270° C. or higher. On the other hand, from the viewpoint of ease of stretching and reduction of the baking temperature, the glass transition temperature is preferably 400° C. or lower, more preferably 380° C. or lower.

[0077] Specifically, examples of polyimide resins include compounds having a structure represented by the following formula: In the formula, n is a repeating unit and represents an integer of 2 or more.

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082]

change

[0083]

change

[0084]

change

[0085]

change

[0086]

change

[0087]

change

[0088]

change

[0089]

change

[0090]

change

[0091]

change

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] Among the above polyimide-based resins, polyimide-based resins or polyamide-based resins having a structure that makes it difficult for intramolecular or intermolecular charge transfer to occur are preferred because they have excellent transparency. Specific examples include fluorinated polyimide-based resins such as those represented by the above formulas (4) to (11) and polyimide-based resins having an alicyclic structure such as those represented by the above formulas (13) to (16).

[0096] Furthermore, the fluorinated polyimide resins such as those represented by the above formulas (4) to (11) have a fluorinated structure, and therefore have high heat resistance and are not discolored by heat during the production of polyimide films made of the polyimide resin, and therefore have excellent transparency.

[0097] The term "polyamide-based resin" refers to a concept that includes not only aliphatic polyamides but also aromatic polyamides (aramids). Polyamide-based resins generally have skeletons represented by the following formulas (21) and (22), and examples of the polyamide-based resins include compounds represented by the following formula (23). In the following formula, n is a repeating unit and represents an integer of 2 or more.

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] The substrate made of the polyimide-based resin or polyamide-based resin represented by the above formulas (4) to (20) and (23) may be commercially available. Examples of commercially available substrates made of the polyimide-based resin include Neoprim manufactured by Mitsubishi Gas Chemical Company, Inc., and examples of commercially available substrates made of the polyamide-based resin include Mictron manufactured by Toray Industries, Inc.

[0102] The substrates made of polyimide or polyamide resins represented by the above formulas (4) to (20) and (23) may be synthesized by known methods. For example, a method for synthesizing the polyimide resin represented by the above formula (4) is described in JP-A-2009-132091, and specifically, the polyimide resin can be obtained by reacting 4,4'-hexafluoropropylidenebisphthalic dianhydride (FPA) represented by the following formula (24) with 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFDB). [ka]

[0103] The weight-average molecular weight of the polyimide resin or polyamide resin is preferably in the range of 3,000 to 500,000, more preferably 5,000 to 300,000, and even more preferably 10,000 to 200,000. If the weight-average molecular weight is less than 3,000, sufficient strength may not be obtained, while if it exceeds 500,000, the viscosity increases and solubility decreases, making it difficult to obtain a substrate with a smooth surface and uniform film thickness. In this specification, the "weight-average molecular weight" is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0104] Among the above polyimide-based resins and polyamide-based resins, polyimide-based resins or polyamide-based resins having a structure that makes it difficult for intramolecular or intermolecular charge transfer to occur are preferred because they have excellent transparency.Specific examples include fluorinated polyimide-based resins such as those represented by the above formulas (4) to (11), polyimide-based resins having an alicyclic structure such as those represented by the above formulas (13) to (16), and polyamide-based resins having a halogen group such as those represented by the above formula (23).

[0105] Furthermore, the fluorinated polyimide resins such as those represented by the above formulas (4) to (11) have a fluorinated structure, and therefore have high heat resistance and are not discolored by heat during the production of a substrate made of a polyimide resin, and therefore have excellent transparency.

[0106] For the light-transmitting substrate 11, a substrate made of a fluorinated polyimide resin represented by any of the above formulas (4) to (11) or a polyamide resin having a halogen group represented by any of the above formulas (23) is preferred, from the viewpoint of being able to achieve a hardness of 3H or more when measured under the pencil hardness test conditions (load: 1 kg, speed: 1 mm / sec) specified in JIS K5600-5-4:1999 on the surface 13A of the inorganic layer 13. Of these, it is more preferred to use a substrate made of a polyimide resin represented by the above formula (4), since this can impart an extremely excellent pencil hardness of 3H or more.

[0107] Examples of polyester resins include resins containing at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate as a constituent component.

[0108] <<Hard Coat Layer>> The hard coat layer 12 has an indentation hardness (H IT The "indentation hardness" in this specification is a value determined from a load-displacement curve from loading to unloading of an indenter, obtained by hardness measurement using a nanoindentation method. The indentation hardness (H ITThe lower limit of the indentation hardness is preferably 200 MPa or more, 500 MPa or more, and 800 MPa or more in that order (the larger the value, the more preferable). The upper limit of the indentation hardness of the hard coat layer 12 is preferably 1500 MPa or less, 1300 MPa or less, and 1100 MPa or less in that order (the smaller the value, the more preferable), from the viewpoint of suppressing breakage or cracking of the hard coat layer 12 when the optical film 10 is folded.

[0109] The indentation hardness (H ITThe measurement of the hard coat thickness is performed on the measurement sample using a HYSITRON TI950 TriboIndenter. Specifically, a 1 mm x 10 mm piece of optical film is first embedded in an embedding resin to prepare a block. A uniform, hole-free section with a thickness of 70 nm to 100 nm is then cut from this block using a standard sectioning method. An Ultramicrotome EM UC7 (Leica Microsystems) or similar instrument can be used to prepare the section. The remaining block from which the uniform, hole-free section is cut serves as the measurement sample. Next, a Berkovich indenter (triangular pyramid, BRUKER TI-0039) is pressed vertically into the cross section of the hard coat layer for 25 seconds with a maximum indentation load of 500 μN under the following measurement conditions: Here, in order to avoid the influence of the light-transmitting substrate and the inorganic layer and the side edges of the hard coat layer, the Berkovich indenter is pressed into a portion of the hard coat layer 500 nm away from the interface between the light-transmitting substrate and the hard coat layer toward the center of the hard coat layer, 500 nm away from the interface between the hard coat layer and the inorganic layer toward the center of the hard coat layer, and 500 nm away from each of the two ends of the hard coat layer toward the center of the hard coat layer. If a functional layer is present between the light-transmitting substrate and the hard coat layer, the Berkovich indenter is pressed into a portion of the hard coat layer 500 nm away from the interface between the functional layer and the hard coat layer toward the center of the hard coat layer, 500 nm away from the interface between the hard coat layer and the inorganic layer toward the center of the hard coat layer, and 500 nm away from each of the two ends of the hard coat layer toward the center of the hard coat layer. Thereafter, the residual stress is relaxed by holding the pressure constant, and then the pressure is released over 25 seconds, and the maximum load after relaxation is measured, and the maximum load P max (μN) and contact projection area A p (nm 2 ) and P max / A p The indentation hardness (H ITThe above contact projected area is the contact projected area corrected for the indenter tip curvature by the Oliver-Pharr method using a standard sample of fused quartz (5-0098 manufactured by BRUKER). Indentation hardness (H IT ) is the arithmetic mean value of the values ​​obtained by measuring at 10 points. If the measured values ​​include values ​​that deviate from the arithmetic mean value by more than ±20%, those values ​​shall be excluded and remeasured. Whether or not there are any measured values ​​that deviate from the arithmetic mean value by more than ±20% shall be judged by whether the value (%) calculated by (AB) / B x 100 is more than ±20%, where A is the measured value and B is the arithmetic mean value. Indentation hardness (H IT ) can be adjusted by the type of binder resin 12A and the content of inorganic particles 12B, which will be described later. (Measurement conditions) ·Loading speed: 20μN / sec ·Holding time: 5 seconds ·Loading and unloading speed: 20μN / sec ·Measurement temperature: 25℃

[0110] The hard coat layer 12 has a thickness of 1 μm or more. If the hard coat layer 12 has a thickness of 1 μm or more, the degree to which steel wool sinks in during a steel wool test is reduced, thereby suppressing scratches on the surface of the hard coat layer. The lower limit of the hard coat layer 12 is preferably 2 μm or more, 3 μm or more, and 4 μm or more in that order (the larger the value, the more preferable). From the viewpoint of obtaining sufficient folding performance, the upper limit of the hard coat layer 12 is preferably 10 μm or less, 9 μm or less, 8 μm or less, and 7 μm or less in that order (the smaller the value, the more preferable).

[0111] The thickness of the hard coat layer is determined by photographing a cross section of the hard coat layer using a scanning transmission electron microscope (STEM) or a transmission electron microscope (TEM). The thickness of the hard coat layer is measured at 10 locations on the cross section image, and the arithmetic mean value of the thicknesses at those 10 locations is used. The specific method for photographing the cross section is described below. First, a 1 mm x 10 mm piece of optical film is embedded in an embedding resin to create a block. From this block, uniform, hole-free slices with a thickness of 70 nm to 100 nm are cut using a standard sectioning method. An "Ultramicrotome EM UC7" (Leica Microsystems) or similar instrument can be used to prepare the slices. These uniform, hole-free slices are used as the measurement sample. Then, a cross-sectional photograph of the measurement sample is taken using a scanning transmission electron microscope (STEM) (product name "S-4800" manufactured by Hitachi High-Technologies Corporation). When taking cross-sectional photographs using the S-4800, the detector is set to "TE," the acceleration voltage is set to "30 kV," and the emission current is set to "10 μA" for cross-sectional observation. The magnification is adjusted appropriately between 5,000x and 200,000x while adjusting the focus and observing whether the contrast and brightness of each layer can be distinguished. The preferred magnification is 10,000x to 100,000x, more preferably 10,000x to 50,000x, and most preferably 25,000x to 50,000x. When taking cross-sectional photographs using the S-4800, the aperture may be set to "beam monitor aperture 3," the objective lens aperture to "3," and the working distance to "8 mm." When measuring the film thickness of a hard coat layer, it is important to observe the interface contrast between the hard coat layer and other layers (e.g., functional layers) as clearly as possible during cross-sectional observation. If the interface is difficult to see due to insufficient contrast, dyeing with osmium tetroxide, ruthenium tetroxide, phosphotungstic acid, or the like can be performed, as this makes the interface between the organic layers easier to see. Furthermore, the contrast of the interface may be more difficult to see at higher magnifications. In such cases, observations should also be made at lower magnifications. For example, observations should be made at two magnifications, such as 25,000x and 50,000x, or 50,000x and 100,000x, and the arithmetic mean value described above is calculated at both magnifications. This mean value is then used as the film thickness value of the hard coat layer.

[0112] The hard coat layer 12 contains a binder resin 12A and inorganic particles 12B. In addition to the binder resin 12A and the inorganic particles 12B, the hard coat layer 12 may contain additives such as an ultraviolet absorber and a spectral transmittance adjuster.

[0113] In the cross section of the hard coat layer 12 in the thickness direction shown in FIG. 2 , the area ratio of inorganic particles 12B in a region IR extending from the interface IF between the hard coat layer 12 and the inorganic layer 13 to a depth of 500 nm into the hard coat layer 12 (hereinafter, this region may be referred to as the “near-interface region”) is preferably 5% or more and 75% or less. If the area ratio of inorganic particles in the near-interface region IF is 5% or more, the hard coat layer 12 contains a large amount of inorganic particles 12B, which makes the hard coat layer 12 harder and improves adhesion to the inorganic layer 13. Furthermore, the steel wool test is performed by applying a load from the surface of the inorganic layer. However, since the surface of the inorganic layer is rubbed with steel wool, a load is applied not only in the thickness direction of the inorganic layer but also in the shear direction. If the area ratio of inorganic particles 12B in the near-interface region IR is 75% or less, even when a load is applied in the shear direction in the steel wool test, the binder resin 12A is present to a certain extent in the hard coat layer 12, making it less susceptible to scratches and abrasion. Furthermore, the presence of a certain amount of binder resin 12A in the hard coat layer 12 can further improve adhesion with the functional layer 14. Here, the area ratio of the inorganic region in the near-interface region is determined because the near-interface region is a region that is particularly susceptible to scratches and abrasion when a steel wool test is performed. The lower limit of the area ratio of the inorganic particles 12B in the near-interface region IF is more preferably 23% or more, 33% or more, and 44% or more (the larger the value, the more preferable). The upper limit of the area ratio of the inorganic particles 12B in the near-interface region IF is more preferably 71% or less, 67% or less, and 60% or less (the smaller the value, the more preferable).

[0114] The area ratio of inorganic particles in the near-interface region is determined as follows. First, a 1 mm x 10 mm optical film is cut and embedded in an embedding resin to create a block. Ten uniform, hole-free sections with a thickness of 70 nm to 100 nm are cut from this block using a standard sectioning method. An Ultramicrotome EM UC7 (Leica Microsystems) or similar can be used to prepare the sections. These 10 uniform, hole-free sections are used as measurement samples. Next, cross-sectional images of each measurement sample are taken using a transmission electron microscope (TEM) or scanning transmission electron microscope (STEM). Cross-sectional images are taken at one location per measurement sample. When taking cross-sectional images of each measurement sample using a scanning transmission electron microscope (STEM) (product name "S-4800" manufactured by Hitachi High-Technologies Corporation), the detector is set to "TE," the acceleration voltage to "30 kV," and the emission current to "10 μA." The magnification is adjusted appropriately between 5,000x and 200,000x while adjusting the focus and observing the contrast and brightness to see if each layer can be distinguished. A preferred magnification is 10,000x to 100,000x, more preferably 10,000x to 50,000x, and most preferably 25,000x to 50,000x. When taking cross-sectional photographs, the aperture may be set to "beam monitor aperture 3," the objective lens aperture to "3," and the WD to "8 mm." Then, for the 10 cross-sectional photographs obtained, the area of ​​the near-interface region is taken as 100%, and the ratio of the area of ​​inorganic particles to the area of ​​the near-interface region (area ratio) is calculated. The area ratio of inorganic particles in the near-interface region is taken as the arithmetic average of the area ratios of inorganic particles calculated from the 10 cross-sectional photographs of the near-interface region. To obtain such an area ratio of inorganic particles 12B, it is preferable to include inorganic particles 12B in a ratio (weight ratio) of 10% to 300% and preferably 10% to 200% of the polymerizable compound that becomes binder resin 12A after curing.

[0115] The surface of the hard coat layer 12 facing the inorganic layer 13 may be treated to expose the inorganic particles 12B, for example, by selectively etching the binder resin 12A. Such treatment can further improve adhesion between the hard coat layer 12 and the inorganic layer 13. However, if this treatment is performed excessively, the surface of the hard coat layer facing the inorganic layer becomes rough and the inorganic layer is thin, so that the surface shape of the hard coat layer is reflected in the surface shape of the inorganic layer. In a steel wool test, the steel wool may get caught on the irregularities present on the surface of the inorganic layer, resulting in reduced scratch resistance. Examples of methods for selectively etching the binder resin include glow discharge treatment, plasma treatment, ion etching treatment, and alkali treatment.

[0116] <Binder resin> The binder resin 12A includes at least one of a polymer (cured product) of a polymerizable compound (curable compound) and a thermoplastic resin. The polymerizable compound has at least one radically polymerizable functional group and one cationically polymerizable functional group in the molecule. Hereinafter, a polymerizable compound having a radically polymerizable functional group will be referred to as a radically polymerizable compound, and a polymerizable compound having a cationically polymerizable functional group will be referred to as a cationically polymerizable compound. Examples of radically polymerizable functional groups include ethylenically unsaturated groups such as (meth)acryloyl groups, vinyl groups, and allyl groups. Note that the term "(meth)acryloyl group" includes both "acryloyl groups" and "methacryloyl groups." Examples of cationically polymerizable functional groups include hydroxyl groups, carboxyl groups, isocyanate groups, amino groups, cyclic ether groups, and mercapto groups.

[0117] The binder resin 12A preferably does not contain 10% by mass or more of polymerizable compounds having a polymerizable functional group equivalent (weight average molecular weight / number of polymerizable functional groups) of 130 or more. By not containing 10% by mass or more of such polymerizable compounds, hardness can be imparted to the hard coat layer 12, so that even when a steel wool test is performed on the surface 10A of the optical film 10, the surface 10A is less likely to be scratched or scraped. Furthermore, the adhesion between the hard coat layer 12 and the functional layer 14 can be further improved.

[0118] The radical polymerizable compound is preferably a polyfunctional (meth)acrylate. Examples of the polyfunctional (meth)acrylate include trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, isocyanuric acid tri(meth)acrylate, isocyanuric acid di(meth)acrylate, polyester tri(meth)acrylate, polyester di(meth)acrylate, bisphenol di(meth)acrylate, diglycerin tetra(meth)acrylate, adamantyl di(meth)acrylate, isoboronyl di(meth)acrylate, dicyclopentane di(meth)acrylate, tricyclodecane di(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and those modified with PO, EO, caprolactone, etc.

[0119] Among these, tri- to hexafunctional compounds are preferred because they can suitably satisfy the above-mentioned indentation hardness, and examples thereof include pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPPA), trimethylolpropane tri(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, etc. In this specification, (meth)acrylate means acrylate and methacrylate.

[0120] The composition may further contain a monofunctional (meth)acrylate monomer in order to adjust the hardness or viscosity of the composition, improve adhesion, etc. Examples of the monofunctional (meth)acrylate monomer include hydroxyethyl acrylate (HEA), glycidyl methacrylate, methoxypolyethylene glycol (meth)acrylate, isostearyl (meth)acrylate, 2-acryloyloxyethyl succinate, acryloylmorpholine, N-acryloyloxyethyl hexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, phenoxyethyl acrylate, and adamantyl acrylate.

[0121] From the viewpoint of improving the hardness of the hard coat layer 12, the weight average molecular weight of the monomer is preferably less than 1,000, and more preferably from 200 to 800. The weight average molecular weight of the polymerizable oligomer is preferably from 1,000 to 20,000, more preferably from 1,000 to 10,000, and even more preferably from 2,000 to 7,000.

[0122] The cationically polymerizable compound is not particularly limited, and examples thereof include epoxy compounds, polyol compounds, isocyanate compounds, melamine compounds, urea compounds, and phenol compounds.

[0123] Examples of thermoplastic resins include styrene-based resins, (meth)acrylic-based resins, vinyl acetate-based resins, vinyl ether-based resins, halogen-containing resins, alicyclic olefin-based resins, polycarbonate-based resins, polyester-based resins, polyamide-based resins, cellulose derivatives, silicone-based resins, and rubber or elastomers.

[0124] <Inorganic particles> The inorganic particles 12B are particles mainly composed of inorganic matter. The inorganic particles 12B may contain an organic component, but are preferably composed of only inorganic matter. The inorganic particles 12B may be surface-treated with an organic component. The inorganic particles 12B are not particularly limited as long as they can improve hardness, but silica particles are preferred from the viewpoint of obtaining excellent hardness.

[0125] Among silica particles, reactive silica particles are preferred. The reactive silica particles are silica particles that can form a crosslinked structure with the polyfunctional (meth)acrylate, and the inclusion of these reactive silica particles can sufficiently increase the hardness of the hard coat layer.

[0126] The reactive silica particles preferably have reactive functional groups on their surfaces, and as the reactive functional groups, for example, the polymerizable functional groups described above are preferably used.

[0127] The reactive silica particles are not particularly limited, and conventionally known particles can be used, such as the reactive silica particles described in JP 2008-165040 A. Commercially available reactive silica particles include MIBK-SD, MIBK-SDMS, MIBK-SDL, and MIBK-SDZL manufactured by Nissan Chemical Industries, Ltd., and V8802 and V8803 manufactured by JGC Catalysts and Chemicals Co., Ltd.

[0128] The silica particles may be spherical, but are preferably irregularly shaped silica particles. In this specification, "spherical silica particles" refers to silica particles such as spherical or ellipsoidal silica particles, and "irregularly shaped silica particles" refers to silica particles with random potato-shaped irregularities on the surface. Since the irregularly shaped silica particles have a larger surface area than spherical silica particles, the inclusion of such irregularly shaped silica particles increases the contact area with the polyfunctional (meth)acrylate, etc., thereby improving the hardness of the hard coat layer. Whether the silica particles are irregularly shaped or not can be confirmed by observing the cross section of the functional layer using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM).

[0129] The average particle diameter of the silica particles is preferably 8 nm or more and 100 nm or less. If the average particle diameter of the silica particles is 8 nm or more, sufficient adhesion to the inorganic layer 13 can be obtained, and if it is 100 nm or less, whitening can be suppressed. The upper limit of the average particle diameter of the silica particles is more preferably 65 nm or less, 40 nm or less, and 25 nm or less, in that order (the smaller the value, the more preferable). When the silica particles are spherical silica particles, the average particle diameter of the silica particles is a value measured using image processing software from images taken with a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM). When the silica particles are irregularly shaped silica particles, the average particle diameter of the silica particles is the average of the maximum (longer diameter) and minimum (minor diameter) distances between two points on the periphery of the irregularly shaped silica particles appearing in images taken with a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM).

[0130] As the silica particles, it is preferable to use a mixture of two or more types of silica particles. For example, the silica particles may be a mixture of the reactive silica particles and non-reactive silica particles, or a mixture of first silica particles and second silica particles having a particle diameter smaller than that of the first silica particles. When the mixture of the reactive silica particles and non-reactive silica particles is used, curling can be suppressed while maintaining adhesion to the inorganic layer 13 and scratch resistance. Furthermore, when the mixture of the first silica particles and second silica particles is used, the hardness of the hard coat layer can be further improved, thereby further improving scratch resistance.

[0131] <UV absorber> Optical films are particularly suitable for use in mobile terminals such as bendable smartphones and tablet terminals, but such mobile terminals are often used outdoors, which poses a problem that a polarizer disposed on the display element side of the optical film is easily exposed to ultraviolet light and deteriorates. In contrast, since the hard coat layer is disposed on the display screen side of the polarizer, if the hard coat layer contains an ultraviolet absorber, deterioration of the polarizer due to exposure to ultraviolet light can be suitably prevented.

[0132] Examples of the ultraviolet absorber include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and benzotriazole-based ultraviolet absorbers.

[0133] Examples of the triazine-based ultraviolet absorber include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6 -(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. Commercially available triazine-based ultraviolet absorbers include TINUVIN 460, TINUVIN 477 (both manufactured by BASF), and LA-46 (manufactured by ADEKA Corporation).

[0134] Examples of the benzophenone-based ultraviolet absorbers include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenone sulfonic acid and its trihydrate, sodium hydroxymethoxybenzophenone sulfonate, etc. Examples of commercially available benzophenone-based ultraviolet absorbers include CHMASSORB81 / FL (manufactured by BASF).

[0135] Examples of the benzotriazole-based ultraviolet absorber include 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-(2H-benzotriazol-2-yl)-6-(straight-chain and branched-chain dodecyl)-4-methylphenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl)benzotriazole, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate. 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-(3'',4'',5'',6''-tetrahydrophthalimidomethyl)-5'-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol), and 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole. Commercially available benzotriazole-based ultraviolet absorbers include, for example, KEMISORB71D and KEMISORB79 (both manufactured by Chemipro Chemical Co., Ltd.), JF-80 and JAST-500 (both manufactured by Johoku Chemical Industry Co., Ltd.), ULS-1933D (manufactured by Lion Specialty Chemicals Co., Ltd.), and RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0136] Among them, triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers are preferably used as ultraviolet absorbers. The ultraviolet absorber preferably has high solubility in the resin components constituting the functional layer, and preferably exhibits little bleed-out after the folding test described above. The ultraviolet absorber is preferably polymerized or oligomerized. The ultraviolet absorber is preferably a polymer or oligomer having a benzotriazole, triazine, or benzophenone skeleton, and more preferably a thermal copolymer of a (meth)acrylate having a benzotriazole or benzophenone skeleton and methyl methacrylate (MMA) in any ratio. When the optical film is applied to an organic light-emitting diode (OLED) display device, the ultraviolet absorber can also protect the OLED from ultraviolet rays.

[0137] The content of the ultraviolet absorber is not particularly limited, but is preferably 1 part by mass or more and 6 parts by mass or less per 100 parts by mass of the solid content of the functional layer composition. If it is less than 1 part by mass, the effect of adding the ultraviolet absorber to the functional layer may not be fully obtained, and if it exceeds 6 parts by mass, the functional layer may be significantly colored or have a reduced strength. The lower limit of the content of the ultraviolet absorber is more preferably 2 parts by mass or more, and the upper limit is more preferably 5 parts by mass or less.

[0138] <Spectral transmittance adjuster> The spectral transmittance adjuster adjusts the spectral transmittance of the optical film. For example, when the hard coat layer 12 contains a sesamol-type benzotriazole monomer represented by the following general formula (21), the above-mentioned spectral transmittance can be suitably satisfied.

[0139] [ka]

[0140] In the formula, R 7 represents a hydrogen atom or a methyl group. 8represents a linear or branched alkylene group having 1 to 6 carbon atoms or a linear or branched oxyalkylene group having 1 to 6 carbon atoms.

[0141] The sesamol-type benzotriazole monomer is not particularly limited, but specific substance names include 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]ethyl methacrylate, 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]ethyl acrylate, 3-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]propyl methacrylate, 3-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]propyl acrylate, 4-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]butyl methacrylate, 4-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]butyl methacrylate, 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yloxy]ethyl acrylate, 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yloxy]ethyl acrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yloxy]ethyl acrylate )-2H-benzotriazol-5-yl}propanoyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]ethyl acrylate, 4-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]butyl methacrylate, 4-[3-{ 2 -(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]butyl acrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,Examples of suitable sesamol-type benzotriazole monomers include 2-(methacryloyloxy)ethyl 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-yl}propanoyloxy)ethyl acrylate, 2-(methacryloyloxy)ethyl 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, 2-(acryloyloxy)ethyl 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, 4-(methacryloyloxy)butyl 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, and 4-(acryloyloxy)butyl 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate. These sesamol-type benzotriazole monomers may be used alone or in combination of two or more.

[0142] When the sesamol-type benzotriazole monomer is contained in the hard coat layer 12, the sesamol-type benzotriazole monomer is preferably contained in an amount of 15 to 30 mass % in the hard coat layer 12. By containing the sesamol-type benzotriazole monomer in such a range, the above-mentioned spectral transmittance can be satisfied. Note that the sesamol-type benzotriazole monomer may be contained integrally in the hard coat layer 12 by reacting with the resin component constituting the hard coat layer 12, or may be contained alone without reacting with the resin component constituting the hard coat layer 12.

[0143] <<Inorganic layer>> The inorganic layer 13 is a layer mainly composed of inorganic materials, and for example, if the inorganic material is present in an inorganic layer at 55 mass % or more, it corresponds to the inorganic layer. The inorganic layer 13 may contain organic components, but is preferably composed only of inorganic materials. Whether or not a layer in contact with the hard coat layer 12 corresponds to the inorganic layer can be confirmed by X-ray photoelectron spectroscopy (XPS) or Electron Spectroscopy for Chemical Analysis (ESCA).

[0144] The inorganic layer 13 may be made of a metal such as Ti, Al, Mg, or Zr, or silicon oxide (SiO x (x=1 to 2)), inorganic oxides such as aluminum oxide, silicon oxynitride, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide, tin oxide, and yttrium oxide, inorganic nitrides, diamond-like carbon, etc. Among these, silicon oxide is preferred from the viewpoint of improving transmittance and scratch resistance.

[0145] The inorganic layer 13 preferably contains silicon. The refractive index of the inorganic layer 13 can be reduced by containing silicon. Whether the inorganic layer contains silicon or not can be confirmed by X-ray photoelectron spectroscopy (XPS) or Electron Spectroscopy for Chemical Analysis (ESCA).

[0146] The thickness of the inorganic layer 13 is preferably 10 nm or more and 300 nm or less. If the thickness of the inorganic layer 13 is 10 nm or more, excellent scratch resistance can be imparted, and if it is 300 nm or less, good adhesion to other layers can be achieved without affecting flexibility or optical properties. The lower limit of the thickness of the inorganic layer 13 is more preferably 30 nm or more, 50 nm or more, and 80 nm or more (the larger the value, the more preferable), and the upper limit is more preferably 250 nm or less, 200 nm or less, and 150 nm or less (the smaller the value, the more preferable). The thickness of the inorganic layer 13 is determined in the same manner as the thickness of the hard coat layer 12.

[0147] The inorganic layer 13 has a water vapor transmission rate (WVTR) of 100 g / (m 2 ·24h) or less. The higher the temperature and relative humidity, the worse the folding resistance. This is thought to be because the inorganic layer 13 allows moisture to pass through, and the permeated moisture causes hydrolysis of the hard coat layer. The water vapor transmission rate of the inorganic layer 13 is preferably 100g / (m 2 By keeping the permeability (times) of the inorganic layer 13 at or below 24 h, the moisture that permeates the inorganic layer 13 can be reduced, thereby suppressing hydrolysis of the hard coat layer. The water vapor permeability is a value obtained by a method conforming to JIS K7129:2008. The water vapor permeability can be measured using a water vapor permeability measuring device (product name "PERMATRAN-W3 / 31", manufactured by MOCON). The water vapor permeability is the average value obtained from three measurements.

[0148] The inorganic layer 13 can be formed by using a vapor deposition method such as a PVD method or a CVD method. Examples of the PVD method include a vacuum deposition method, a sputtering method, and an ion plating method. Examples of the vacuum deposition method include a vacuum deposition method using an electron beam (EB) heating method or a vacuum deposition method using a high-frequency dielectric heating method.

[0149] <<Function layer>> The functional layer 14 is a layer that exhibits some function in the optical film 10, and examples of the functional layer 14 include an optical adjustment layer and an antistatic layer. The functional layer 14 may exhibit two or more functions. For example, the functional layer 14 may be a layer that exhibits both an optical adjustment function and an antistatic function.

[0150] The thickness of the functional layer 14 is preferably 30 nm or more and 200 nm or less. If the thickness of the functional layer 14 is 30 nm or more, sufficient adhesion between the hard coat layer 12 and the optical adjustment layer 14 can be ensured, and if the thickness is 200 nm or less, interference fringes can be further suppressed. The lower limit of the functional layer 14 is more preferably 50 nm or more, 70 nm or more, and 90 nm or more (the larger the value, the more preferable), and the upper limit is more preferably 150 nm or less, 140 nm or less, and 130 nm or less (the smaller the value, the more preferable). The thickness of the functional layer 14 is determined in the same manner as the thickness of the hard coat layer 12.

[0151] <Optical adjustment layer> Generally, the resin constituting a bendable light-transmitting substrate has a high refractive index, resulting in a large difference in refractive index between the light-transmitting substrate and the hard coat layer. This difference in refractive index between the light-transmitting substrate and the hard coat layer can result in the occurrence of interference fringes, iridescent irregularities. The optical adjustment layer is a layer designed to suppress the occurrence of interference fringes. From the perspective of suppressing the occurrence of interference fringes, the refractive index of the optical adjustment layer is preferably lower than that of the light-transmitting substrate 11 and higher than that of the hard coat layer 12. The refractive index of the optical adjustment layer can be measured, for example, by the Becke method. When measuring the refractive index of the optical adjustment layer using the Becke method, ten pieces of the optical adjustment layer are cut out, and the refractive index of each of the ten cut pieces is measured using a refractive index standard solution by the Becke method. The average of the ten measured refractive indices is taken as the refractive index of the optical adjustment layer. The refractive index of the light-transmitting substrate 11 and the hard coat layer 12 can also be measured using the same method as the refractive index of the optical adjustment layer.

[0152] The refractive index difference between the optical adjustment layer and the hard coat layer 12 (refractive index of the optical adjustment layer - refractive index of the hard coat layer) is preferably 0.005 or more and 0.100 or less. If this refractive index difference is 0.005 or more, interfacial reflection occurs between the optical adjustment layer and the hard coat layer 12, but interference fringes can be made invisible. If this refractive index difference is 0.100 or less, interference fringes can be slightly observed, but can be made to a level that does not cause problems in practical use. The lower limit of this refractive index difference is more preferably 0.007 or more, and the upper limit is more preferably 0.090 or less. The refractive index of the optical adjustment layer may be 0.010 or more and 0.080 or less.

[0153] The optical adjustment layer may be composed solely of resin, but preferably contains a binder resin and particles for adjusting the refractive index. Furthermore, the optical adjustment layer may further contain an antistatic agent to provide antistatic properties in addition to the optical adjustment function. The binder resin of the optical adjustment layer is preferably at least one resin selected from the group consisting of (meth)acrylic resins, cellulose resins, urethane resins, vinyl chloride resins, polyester resins, polyolefin resins, polycarbonate, nylon, polystyrene, and ABS resins. The particles of the optical adjustment layer 14 are preferably at least one selected from the group consisting of low-refractive-index particles such as silica and magnesium fluoride, metal oxide particles such as titanium oxide and zirconium oxide, and inorganic pigments such as cobalt blue. Among these, a combination of polyester resin and metal oxide particles such as titanium oxide and zirconium oxide is more preferred from the viewpoints of adhesion and refractive index difference adjustment.

[0154] <Antistatic layer> The antistatic layer contains an antistatic agent, which may be an ion-conductive antistatic agent or an electron-conductive antistatic agent, and the ion-conductive antistatic agent is preferred from the viewpoint of compatibility with the binder resin.

[0155] Examples of the ion-conducting antistatic agent include cationic antistatic agents such as quaternary ammonium salts and pyridium salts, anionic antistatic agents such as alkali metal salts of sulfonic acid, phosphoric acid, carboxylic acid, etc. (e.g., lithium salts, sodium salts, potassium salts, etc.), amphoteric antistatic agents such as amino acid-based and amino acid sulfate-based, and nonionic antistatic agents such as amino alcohol-based, glycerin-based, and polyethylene glycol-based. Among these, quaternary ammonium salts and lithium salts are preferred because they exhibit excellent compatibility with binder resins.

[0156] Examples of the electron-conductive antistatic agent include conductive polymers such as polyacetylene and polythiophene, metal particles, and conductive particles such as metal oxide particles. Among these, antistatic agents in which a dopant is combined with a conductive polymer such as polyacetylene or polythiophene, metal particles, and metal oxide particles are preferred. Furthermore, the conductive particles can also be incorporated into the conductive polymer.

[0157] Specific examples of the antistatic agent made of the conductive polymer include conductive polymers such as polyacetylene, polyaniline, polythiophene, polypyrrole, polyphenylene sulfide, poly(1,6-heptadiyne), polybiphenylene (polyparaphenylene), polyparaphenylene sulfide, polyphenylacetylene, poly(2,5-thienylene), and derivatives thereof, and preferably, polythiophene-based conductive organic polymers (e.g., 3,4-ethylenedioxythiophene (PEDOT)) are used.

[0158] By using the antistatic agent made of the conductive organic polymer, the antistatic property can be maintained for a long period of time with little humidity dependency, high transparency and low haze value can be realized, and further, high hard coat properties, particularly pencil hardness and scratch resistance to steel wool and the like can be significantly improved.

[0159] The metal constituting the metal particles is not particularly limited, and examples thereof include Au, Ag, Cu, Al, Fe, Ni, Pd, Pt, etc., alone or alloys of these metals. The metal oxide constituting the metal oxide particles is also not particularly limited, and examples thereof include tin oxide (SnO), antimony oxide (SbO), antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), aluminum-doped zinc oxide (AZO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), etc.

[0160] The content of the antistatic agent is not particularly limited, but is preferably 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the polymerizable compound of the antistatic layer composition. If it is 1 part by mass or more, the above-mentioned antistatic properties can be sufficiently obtained, and if it is 50 parts by mass or less, a highly transparent film with a small haze value and good total light transmittance can be obtained. The lower limit of the content of the antistatic agent is more preferably 10 parts by mass or more, and the upper limit is more preferably 40 parts by mass or less.

[0161] <<Optical film manufacturing method>> The optical film 10 can be produced, for example, as follows: First, a functional layer composition for forming the functional layer 14 is applied to one surface of the light-transmitting substrate 11 using a coating device such as a bar coater to form a coating film of the functional layer composition. Note that the functional layer composition here is a composition for an optical adjustment layer, but it may also be a composition for an antistatic layer.

[0162] <Composition for functional layer> The functional layer composition contains a binder resin precursor, particles such as metal oxide, and a solvent. The functional layer composition may also contain, as needed, at least one of low-refractive-index particles such as silica or magnesium fluoride, inorganic pigments such as cobalt blue, a leveling agent, and a polymerization initiator. Furthermore, when a polyester resin is used as the binder resin precursor, the functional layer composition may also contain, as needed, one or more resins selected from the group consisting of (meth)acrylic resins, cellulose resins, urethane resins, vinyl chloride resins, polyolefin resins, polycarbonates, nylons, polystyrenes, and ABS resins.

[0163] After forming a coating film of the functional layer composition, the coating film is dried by various known methods, for example by heating it at a temperature of 40°C or higher and 200°C or lower for 10 to 120 seconds, to evaporate the solvent or harden it, and if necessary, the coating film is irradiated with ionizing radiation such as ultraviolet light to form functional layer 14.

[0164] After forming the functional layer 14, a hard coat layer composition for forming the hard coat layer 12 is applied onto the functional layer 14 using a coating device such as a bar coater to form a coating film of the hard coat layer composition.

[0165] <Hard Coat Layer Composition> The composition for a hard coat layer contains a polymerizable compound that becomes a binder resin 12A after curing and inorganic particles 12B. The composition for a hard coat layer may also contain an ultraviolet absorber, a spectral transmittance adjuster, a leveling agent, a solvent, and a polymerization initiator, as necessary.

[0166] (solvent) Examples of the solvent include alcohols (e.g., methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol, and diacetone alcohol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone, and diacetone alcohol), esters (methyl acetate, ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, and methyl formate), and Examples of suitable solvents include methyl isobutyl ketone and methyl ethyl ketone (PGMEA), aliphatic hydrocarbons (e.g., hexane and cyclohexane), halogenated hydrocarbons (e.g., methylene chloride, chloroform and carbon tetrachloride), aromatic hydrocarbons (e.g., benzene, toluene and xylene), amides (e.g., dimethylformamide, dimethylacetamide and n-methylpyrrolidone), ethers (e.g., diethyl ether, dioxane and tetrahydrofuran), ether alcohols (e.g., 1-methoxy-2-propanol), and carbonates (dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate). These solvents may be used alone or in combination of two or more. Among these, methyl isobutyl ketone and methyl ethyl ketone are preferred as the solvents, as they can dissolve or disperse components such as urethane (meth)acrylate and other additives and allow the resin layer composition to be suitably applied.

[0167] (Polymerization initiator) The polymerization initiator is a component that is decomposed by irradiation with ionizing radiation or heat to generate radicals and initiate or advance the polymerization (crosslinking) of the polymerizable compound.

[0168] The polymerization initiator is not particularly limited as long as it is capable of releasing a substance that initiates radical polymerization upon exposure to ionizing radiation or heat. The polymerization initiator is not particularly limited, and known initiators can be used, specific examples of which include acetophenones, benzophenones, Michler's benzoyl benzoate, α-amyloxime ester, thioxanthones, propiophenones, benzils, benzoins, and acylphosphine oxides. It is also preferable to use a photosensitizer in combination, specific examples of which include n-butylamine, triethylamine, and poly-n-butylphosphine.

[0169] After forming a coating film of the composition for a hard coat layer, the coating film is dried by various known methods, for example, by heating at a temperature of 30°C or higher and 120°C or lower for 10 to 120 seconds, to evaporate the solvent.

[0170] After the coating film is dried, the coating film is irradiated with ionizing radiation such as ultraviolet light to harden the coating film, thereby forming the hard coat layer 12.

[0171] After forming the hard coat layer 12, the inorganic layer 13 is formed by a vapor deposition method such as sputtering so as to be in contact with the hard coat layer 12. In this way, the optical film 10 shown in FIG.

[0172] <<<Image display devices>>> The optical film 10 can be incorporated into a foldable image display device for use. Fig. 4 is a schematic diagram of an image display device according to this embodiment. As shown in Fig. 4, an image display device 40 mainly includes a housing 41 accommodating a battery and other components, a protective film 42, a display panel 43, a touch sensor 44, a circular polarizer 45, and an optical film 10 stacked in this order facing the viewer. Light-transmitting adhesive layers 46, such as OCA (Optical Clear Adhesive), are disposed between the display panel 43 and the touch sensor 44, between the touch sensor 44 and the circular polarizer 45, and between the circular polarizer 45 and the optical film 10, and these components are fixed to each other by the light-transmitting adhesive layers 46.

[0173] The optical film 10 is disposed so that the hard coat layer 12 is closer to the viewer than the light-transmitting substrate 11. In the image display device 40, the surface 10A of the optical film 10 constitutes the surface 40A of the image display device 40.

[0174] In the image display device 40, the display panel 43 is an organic light-emitting diode panel including organic light-emitting diodes and the like. The touch sensor 44 is disposed closer to the display panel 43 than the circular polarizer 45, but may be disposed between the circular polarizer 45 and the optical film 10. The touch sensor 44 may be of an on-cell type or an in-cell type.

[0175] The present inventors conducted extensive research into the scratch resistance of optical films having an inorganic layer formed on a hard coat layer and found that scratch resistance can be improved by incorporating inorganic particles into the hard coat layer, setting the hard coat layer thickness to 1 μm or more, and setting the indentation hardness of the hard coat layer to 200 MPa or more. This is believed to be because blending appropriate inorganic particles into an appropriate hard coat layer ensures adhesion to the inorganic layer and achieves high hardness of the hard coat layer. According to this embodiment, the hard coat layer 12 containing the binder resin 12A and the inorganic particles 12B has a thickness of 1 μm or more and an indentation hardness of the hard coat layer 12 to 200 MPa or more, thereby providing an optical film 10 with excellent scratch resistance.

[0176] When a steel wool test is performed on the surface of the hard coat layer, the inorganic particles tend to fall off. For this reason, from the viewpoint of improving scratch resistance, it is considered preferable that the hard coat layer does not contain inorganic particles. However, in this embodiment, the inorganic layer 13 is formed on the hard coat layer 12, and therefore, the inorganic particles 12B in the hard coat layer 12 can be prevented from falling off during the steel wool test. Thus, by including the inorganic particles 12, the hardness of the hard coat layer 12 can be increased, and the scratch resistance can be improved.

[0177] [Second embodiment] An optical film and an image display device according to a second embodiment of the present invention will be described below with reference to the drawings. Fig. 5 is a schematic diagram of the optical film according to this embodiment. In Fig. 5, components denoted by the same reference numerals as in Fig. 1 are the same as those shown in Fig. 1, and therefore their description will be omitted.

[0178] <<<Optical Films>>> 5 includes, in the same order as the optical film 10, a light-transmitting substrate 11, a hard coat layer 51, and an inorganic layer 13. In FIG. 5, the surface 50A of the optical film 50 is the surface 13A of the inorganic layer 13, and the back surface 50B is the surface of the light-transmitting substrate 11 opposite to the surface on the hard coat layer 51 side. The physical properties of the optical film 50 are similar to those of the optical film 10, and therefore will not be described here.

[0179] <<Hard Coat Layer>> For the same reasons as those explained in the section on hard coat layer 12, hard coat layer 51 has an indentation hardness of 200 MPa or more and a film thickness of 1 μm or more. The preferred upper and lower limits of the indentation hardness and film thickness of hard coat layer 51 are the same as those of hard coat layer 12. Note that other physical properties of hard coat layer 51 are the same as those of hard coat layer 12, and therefore will not be described here.

[0180] The hard coat layer 51 contains at least one of a metal element and a metalloid element. By including at least one of a metal element and a metalloid element in the hard coat layer 51, adhesion to the inorganic layer 13 can be improved, thereby improving scratch resistance. Examples of metal elements include typical metal elements such as aluminum and tin, and transition metal elements such as zirconium and titanium. Examples of metalloid elements include boron, silicon, germanium, arsenic, antimony, and tellurium. Whether the hard coat layer contains the above elements can be confirmed by the following method. First, an optical film cut into a size of 1 mm x 6 mm is cut with a microtome (product name "Ultramicrotome EM UC7" manufactured by Leica Microsystems) at an angle of 2° or less relative to the in-plane direction to a depth greater than the thickness of the inorganic layer, thereby exposing the hard coat layer. Then, elemental analysis is performed on the surface obtained by the cutting using an X-ray photoelectron spectroscopy analyzer (product name "KRATOS Nova" manufactured by Shimadzu Corporation). This makes it possible to confirm whether the hard coat layer contains at least one of a metal element and a metalloid element.

[0181] The total atomic ratio of the metal elements and metalloid elements contained in the hard coat layer 51, as measured by X-ray photoelectron spectroscopy, is preferably 1.5% or more and 30% or less. When the total atomic ratio of the metal elements and metalloid elements is 1.5% or more, adhesion to the inorganic layer 13 can be further improved, and when it is 30% or less, flexibility can be maintained. The total atomic ratio of the metal elements and metalloid elements is measured using an X-ray photoelectron spectroscopy analyzer (ESCA, product name "KRATOS Nova", manufactured by Shimadzu Corporation) on the surface obtained by cutting for the elemental analysis. The lower limit of the atomic ratio of the total amount of the metal elements and metalloid elements in the hard coat layer 51 is preferably 2% or more and 5% or more (the larger the value, the better), and the upper limit is preferably 25% or less and 20% or less (the smaller the value, the better).

[0182] The hard coat layer 51 preferably contains a silicone resin 51A and inorganic particles 51B to further improve scratch resistance. However, as long as the hard coat layer 51 contains at least one of a metal element and a metalloid element, it does not need to contain both the silicone resin 51A and the inorganic particles 51B. For example, if the hard coat layer contains a silicone resin, the hard coat layer does not need to contain inorganic particles 51B because it contains silicon derived from the silicone resin. Also, if the hard coat layer contains silica particles as inorganic particles, the hard coat layer does not need to contain a silicone resin because it contains silicon derived from the silica particles. In this specification, "silicone resin" refers to a polymer compound having a main skeleton formed by a siloxane bond (a bond between silicon and oxygen). In addition to the silicone resin 51A and the inorganic particles 51B, the hard coat layer 51 may contain additives such as an ultraviolet absorber and a spectral transmittance adjuster.

[0183] <Silicone resin> The silicone resin 51A may be a silicone resin having a polymerizable functional group represented by the general formula (R 9 SiO 1.5 ) n In the above formula, it is preferable that the polymer (cured product) is a polymer of a polymerizable compound containing silsesquioxane represented by the formula: 9 is a polymerizable functional group such as a radically polymerizable functional group or a cationically polymerizable functional group, and n is an integer of 1 or greater. The polymerizable compound may contain other polymerizable compounds in addition to the silsesquioxane, or may consist solely of the silsesquioxane. When silicone resin 51A contains a polymer of a polymerizable compound containing such a silsesquioxane, adhesion to the inorganic layer can be further ensured. Examples of radically polymerizable functional groups include ethylenically unsaturated groups such as (meth)acryloyl groups, vinyl groups, and allyl groups, and examples of cationically polymerizable functional groups include epoxy groups and oxetanyl groups. By including such radically polymerizable functional groups or cationically polymerizable functional groups, silsesquioxanes can be linked together to obtain a polymer.

[0184] The structure of the silsesquioxane is not particularly limited, and examples thereof include cage structures such as complete cage structures and incomplete cage structures, ladder structures, random structures, etc. Commercially available silsesquioxane products include Glycidyl polysilsesquioxane cage mixture manufactured by Constur Chemical Co., Ltd. and the photocurable SQ series manufactured by Toagosei Co., Ltd.

[0185] The polymerizable compound forming silicone resin 51A may contain, instead of the silsesquioxane, a dimethylpolysiloxane having a radically polymerizable functional group such as a (meth)acryloyl group, a silicone oligomer having an alkoxysilyl group, and / or a silicone polymer, etc. From the viewpoint of further increasing the hardness of the hard coat layer, the silicone oligomer or silicone polymer preferably has a polymerizable functional group such as a radically polymerizable functional group or a cationically polymerizable functional group.

[0186] Commercially available dimethylpolysiloxanes having a radically polymerizable functional group include the KR series manufactured by Shin-Etsu Chemical Co., Ltd., such as KP-410, KP-411, KP-412, KP-413, KP-414, KP-415, and KP-423 (all of which are double-end types), KP-416, KP-418, and KP-422 (all of which are single-end types), and KP-420 (side chain type).

[0187] Commercially available silicone oligomers having alkoxysilyl groups include, for example, KR-500, KR-515, KC-895, and X-40-9225 manufactured by Shin-Etsu Chemical Co., Ltd. Furthermore, examples of ultra-high molecular weight silicone resins include, for example, KR-251 manufactured by Shin-Etsu Chemical Co., Ltd.

[0188] <Inorganic particles> The inorganic particles 51B are similar to the inorganic particles 12B described in the first embodiment, and therefore, a description thereof will be omitted here.

[0189] The present inventors have conducted extensive research into the scratch resistance of optical films having an inorganic layer formed on a hard coat layer, and have found that scratch resistance can be improved by incorporating at least one of a metal element and a metalloid element into the hard coat layer, setting the thickness of the hard coat layer to 1 μm or more, and setting the indentation hardness of the hard coat layer to 200 MPa or more. This is believed to be because incorporating at least one of a metal element and a metalloid element into the hard coat layer ensures adhesion to the inorganic layer and achieves high hardness of the hard coat layer. According to this embodiment, an optical film 50 having excellent scratch resistance can be provided by incorporating at least one of a metal element and a metalloid element into the hard coat layer 51, setting the thickness of the hard coat layer 51 to 1 μm or more, and setting the indentation hardness of the hard coat layer 51 to 200 MPa or more.

[0190] When a steel wool test is performed on the surface of the hard coat layer, the inorganic particles tend to fall off. For this reason, from the viewpoint of improving scratch resistance, it is considered preferable that the hard coat layer does not contain inorganic particles. However, in this embodiment, the inorganic layer 13 is formed on the hard coat layer 51, and therefore, the inorganic particles 51B in the hard coat layer 51 can be prevented from falling off during the steel wool test. Thus, by including the inorganic particles 51B, the hardness of the hard coat layer 51 can be increased, and the scratch resistance can be improved.

[0191] <<<Image display devices>>> The optical film 50 can be incorporated into a foldable image display device for use. FIG. 6 is a schematic diagram of an image display device according to this embodiment. The image display device 60 shown in FIG. 6 includes the optical film 50. The image display device 60 is similar to the image display device 40 except that the optical film 10 is replaced with the optical film 50, and therefore a description thereof will be omitted here. [Example]

[0192] In order to explain the present invention in detail, the following examples are given, but the present invention is not limited to these examples. Note that the "value calculated based on 100% solids content" below refers to a value when the solids content in the solvent-diluted product is taken as 100%.

[0193] <Preparation of hard coat layer composition> First, the components were blended to obtain the composition shown below to obtain a composition for an optical adjustment layer. (Hard Coat Layer Composition 1) Polyester acrylate (product name "M-9050", manufactured by Toagosei Co., Ltd.): 50 parts by weight Silica particles (product name "MIBK-SD", manufactured by Nissan Chemical Industries, Ltd.): 50 parts by mass Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacure (registered trademark) 184", manufactured by BASF Japan Ltd.): 5 parts by mass Methyl isobutyl ketone: 100 parts by weight

[0194] (Hard Coat Layer Composition 2) Polyester acrylate (product name "M-9050", manufactured by Toagosei Co., Ltd.): 67 parts by weight Silica particles (product name "MIBK-SD", manufactured by Nissan Chemical Industries, Ltd.): 33 parts by mass Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacure (registered trademark) 184", manufactured by BASF Japan Ltd.): 5 parts by mass Methyl isobutyl ketone: 100 parts by weight

[0195] (Hard Coat Layer Composition 3) Polyester acrylate (product name "M-9050", manufactured by Toagosei Co., Ltd.): 90 parts by weight Silica particles (product name "MIBK-SD", manufactured by Nissan Chemical Industries, Ltd.): 10 parts by mass Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacure (registered trademark) 184", manufactured by BASF Japan Ltd.): 5 parts by mass Methyl isobutyl ketone: 100 parts by weight

[0196] (Hard Coat Layer Composition 4) Alkoxylated dipentaerythritol acrylate (product name "A-DPH-12E", manufactured by Shin-Nakamura Chemical Co., Ltd.): 50 parts by mass Silica particles (product name "MIBK-SD", manufactured by Nissan Chemical Industries, Ltd.): 50 parts by mass Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacure (registered trademark) 184", manufactured by BASF Japan Ltd.): 5 parts by mass Methyl isobutyl ketone: 100 parts by weight

[0197] (Hard Coat Layer Composition 5) Glycidyl polysilsesquioxane (product name: "Glycidyl polysilsesquioxane cage mixture", manufactured by Constur Chemical Co., Ltd.): 100 parts by mass Polymerization initiator (tri-p-tolylsulfonium hexafluorophosphate, manufactured by Tokyo Chemical Industry Co., Ltd.): 5 parts by mass 1-Methoxy-2-propanol: 100 parts by mass

[0198] (Hard Coat Layer Composition 6) Polyester acrylate (product name "M-9050", manufactured by Toagosei Co., Ltd.): 100 parts by weight Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacure (registered trademark) 184", manufactured by BASF Japan Ltd.): 5 parts by mass Methyl isobutyl ketone: 100 parts by weight

[0199] (Hard Coat Layer Composition 7) Polypropylene glycol diacrylate (product name "M-220", manufactured by Toagosei Co., Ltd.): 90 parts by weight Silica particles (product name "MIBK-SD", manufactured by Nissan Chemical Industries, Ltd.): 10 parts by mass Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacure (registered trademark) 184", manufactured by BASF Japan Ltd.): 5 parts by mass Methyl isobutyl ketone: 100 parts by weight

[0200] <Preparation of composition for optical adjustment layer> The components were blended so as to obtain the composition shown below, thereby obtaining a composition for an optical adjustment layer. (Composition 1 for optical adjustment layer) Urethane-modified polyester resin (product name "UR-3200", manufactured by Toyobo Co., Ltd.): 85 parts by weight (based on 100% solids) Zirconium oxide (average particle size 20 nm, manufactured by CIK Nanotech Co., Ltd.): 15 parts by weight (based on 100% solids) Methyl isobutyl ketone (MIBK): 170 parts by weight

[0201] <Preparation of polyimide substrate> A solution of 278.0 g of dehydrated dimethylacetamide and 8.1 g (33 mmol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (AprTMOS) dissolved in a 500 ml separable flask was maintained at a liquid temperature of 30°C, and 18.1 g (41 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) was gradually added thereto so that the temperature did not rise by more than 2°C, and the solution was stirred with a mechanical stirrer for 1 hour. To this was added 46.1 g (131 mmol) of 2,2'-bis(trifluoromethyl)benzidine (TFMB), and after confirming that it had completely dissolved, 51.8 g (122 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) was gradually added in several portions so that the temperature rise was kept at 2°C or less, synthesizing a polyimide precursor solution (1) (solid content 30 wt%) in which polyimide precursor 1 had been dissolved.

[0202] The polyimide precursor solution (1) was cooled to room temperature, and 196.8 g of dehydrated dimethylacetamide was added and stirred until homogeneous. Next, 128.9 g (1.63 mol) of pyridine catalyst and 167.7 g (1.63 mol) of acetic anhydride were added and stirred at room temperature for 24 hours to synthesize a polyimide solution. 400.0 g of the resulting polyimide solution was transferred to a 5 L separable flask, and 119.2 g of butyl acetate was added and stirred until homogeneous. Next, 688.0 g of methanol was gradually added to obtain a slightly turbid solution. 2.064 kg of methanol was added all at once to the turbid solution to obtain a white slurry. The slurry was filtered and washed five times with methanol to obtain 65.0 g of polyimide resin (1).

[0203] 10.0 g of the polyimide resin (1) was added to 42.2 g of butyl acetate and stirred at room temperature for 1 hour to obtain a polyimide solution. The polyimide solution was degassed for 10 minutes in a tabletop ultrasonic cleaner (product name "UT-104", manufactured by Sharp Corporation), removed, and allowed to stand at room temperature for 1 hour. The polyimide solution was then applied to a 250 μm-thick polyethylene terephthalate (PET) film (product name "Lumirror T60", manufactured by Toray Industries, Inc.), dried for 10 minutes in a circulating oven at 40°C and 10 minutes at 150°C, then peeled from the PET film and further dried for 1 hour at 150°C to obtain a polyimide substrate measuring A5 size (148 mm x 210 mm) and 50 μm thick. The thickness of the polyimide substrate was measured by photographing the cross section of the polyimide substrate using a scanning electron microscope (SEM). The thickness of the polyimide substrate was measured at 10 points on the cross section and the arithmetic mean value of the film thicknesses at those 10 points was used.

[0204] Example 1 A polyimide substrate (product name "Neoprim", manufactured by Mitsubishi Gas Chemical Company, Inc.) with a refractive index of 1.630 and a thickness of 50 μm was prepared as a light-transmitting substrate, and composition 1 for hard coat layers was applied to one side of the polyimide substrate using a bar coater to form a coating film. The formed coating film was then heated at 70°C for 1 minute to evaporate the solvent in the coating film, and ultraviolet light was irradiated in a nitrogen atmosphere using an ultraviolet irradiation device (light source H bulb, manufactured by Fusion UV Systems Japan Co., Ltd.) at an integrated light dose of 200 mJ / cm. 2 The coating was cured by irradiating the coating with light so that a hard coat layer having a refractive index of 1.521 and a thickness of 4 μm was formed. Finally, a 100 nm thick SiO 2 film was deposited on the surface of the hard coat layer by a sputtering method. x (x=1 to less than 2) was formed, thereby obtaining an optical film.

[0205] The thickness of the polyimide substrate was measured by photographing the cross section of the polyimide substrate using a scanning electron microscope (SEM). The thickness of the polyimide substrate was measured at 10 locations on the cross-sectional image, and the arithmetic mean value of the 10 thicknesses was used. The thickness of the hard coat layer was measured by photographing the cross section of the hard coat layer using a scanning transmission electron microscope (STEM) (product name "S-4800" manufactured by Hitachi High-Technologies Corporation). The thickness of the hard coat layer was measured at 10 locations on the cross-sectional image, and the arithmetic mean value of the 10 thicknesses was used. Cross-sectional photographs of the hard coat layer were taken as follows. First, a 1 mm × 10 mm optical film was embedded in an embedding resin to prepare a block. Hole-free, uniform slices with a thickness of 70 nm to 100 nm were cut from this block using a conventional sectioning method. The slices were prepared using an "Ultramicrotome EM UC7" (Leica Microsystems) or the like. These hole-free, uniform slices were used as measurement samples. Cross-sectional images of the samples were then taken using a scanning transmission electron microscope (STEM). The cross-sectional images were taken using STEM observation with the detector set to "TE," the acceleration voltage set to "30 kV," and the emission current set to "10 μA." The magnification was adjusted appropriately from 5,000x to 200,000x while adjusting the focus and contrast and brightness to determine whether each layer could be distinguished. Furthermore, the aperture was set to "beam monitor stop 3," the objective lens stop to "3," and the working distance to "8 mm" when taking the cross-sectional images. The thickness of the inorganic layer was measured using the same method as for the hard coat layer. The refractive indices of the polyimide substrate and hard coat layer were determined using the Becke method in accordance with JIS K7142:2008, Method B. When the refractive index of the polyimide substrate is determined by the Becke method, 10 pieces of the polyimide substrate are cut out, and the refractive index of each of the 10 cut pieces is measured using the sodium D line at a wavelength of 589 nm and a refractive index standard solution, and the average value of the 10 measured refractive indexes is taken as the refractive index of the polyimide substrate. When the refractive index of the hard coat layer is determined by the Becke method, it is determined by the same method as that of the polyimide substrate by the Becke method.In Examples 2 to 7 and Comparative Examples 1 to 4, the thickness and refractive index of the polyimide-based substrate and the like were measured in the same manner as in Example 1.

[0206] <Example 2> In Example 2, an optical film was obtained in the same manner as in Example 1, except that composition 2 for a hard coat layer was used instead of composition 1 for a hard coat layer.

[0207] Example 3 In Example 3, an optical film was obtained in the same manner as in Example 1, except that composition 3 for a hard coat layer was used instead of composition 1 for a hard coat layer.

[0208] Example 4 In Example 4, an optical film was obtained in the same manner as in Example 1, except that composition 4 for a hard coat layer was used instead of composition 1 for a hard coat layer.

[0209] <Example 5> In Example 5, an optical film was obtained in the same manner as in Example 1, except that the thickness of the hard coat layer was changed to 2 μm.

[0210] Example 6 In Example 6, an optical film was obtained in the same manner as in Example 1, except that the thickness of the hard coat layer was changed to 10 μm.

[0211] Example 7 In Example 7, an optical film was obtained in the same manner as in Example 1, except that the thickness of the hard coat layer was changed to 20 μm.

[0212] Example 8 A polyimide substrate (product name "Neoprim", manufactured by Mitsubishi Gas Chemical Company, Inc.) with a refractive index of 1.630 and a thickness of 50 μm was prepared as the light-transmitting substrate. Composition 1 for optical adjustment layer was applied to one side of the polyimide substrate using a bar coater to form a coating film. The formed coating film was then heated at 90°C for 1 minute to evaporate the solvent in the coating film, forming an optical adjustment layer with a refractive index of 1.562 and a thickness of 100 nm. After forming the optical adjustment layer, Composition 1 for hard coat layer was applied to the surface of the optical adjustment layer using a bar coater to form a coating film. The formed coating film was then heated at 70°C for 1 minute to evaporate the solvent in the coating film, and ultraviolet light was applied to the surface of the optical adjustment layer using an ultraviolet irradiation device (light source H bulb, manufactured by Fusion UV Systems Japan Co., Ltd.) at an integrated light intensity of 200 mJ / cm in a nitrogen atmosphere. 2 The coating was cured by irradiating the coating with light so that a hard coat layer having a refractive index of 1.521 and a thickness of 4 μm was formed. Finally, a 100 nm thick SiO 2 film was deposited on the surface of the hard coat layer by a sputtering method. x (x=1 to less than 2) was formed to obtain an optical film. The thickness of the optical adjustment layer was also measured by photographing the cross section of the optical adjustment layer using a scanning transmission electron microscope (STEM) (product name "S-4800", manufactured by Hitachi High-Technologies Corporation), measuring the thickness of the optical adjustment layer at 10 points on each cross section image, and using the arithmetic mean value of the thicknesses at those 10 points. The thickness of the optical adjustment layer was measured using the same method as for the thickness of the hard coat layer. The refractive index of the optical adjustment layer was also measured using the Becke method in accordance with Method B of JIS K7142:2008, as with polyimide-based substrates, etc.

[0213] Example 9 In Example 9, an optical film was obtained in the same manner as in Example 1, except that the polyimide base material 1 prepared above was used as the polyimide base material (product name "Neoprim", manufactured by Mitsubishi Gas Chemical Company, Inc.).

[0214] Example 10 In Example 10, an optical film was obtained in the same manner as in Example 1, except that composition 5 for a hard coat layer was used instead of composition 1 for a hard coat layer.

[0215] <Comparative Example 1> In Comparative Example 1, an optical film was obtained in the same manner as in Example 1, except that Composition 6 for a hard coat layer was used instead of Composition 1 for a hard coat layer.

[0216] <Comparative Example 2> In Comparative Example 2, an optical film was obtained in the same manner as in Example 1, except that Composition 7 for a hard coat layer was used instead of Composition 1 for a hard coat layer.

[0217] <Comparative Example 3> In Comparative Example 3, an optical film was obtained in the same manner as in Example 1, except that the thickness of the hard coat layer was changed to 0.8 μm.

[0218] <Indentation hardness measurement> The indentation hardness of the hard coat layer of the optical film according to the examples and comparative examples was measured. Specifically, a 1 mm × 10 mm piece of optical film was first embedded in an embedding resin to prepare a block. A uniform, hole-free section with a thickness of 70 nm to 100 nm was then cut from this block using a standard sectioning method. An "Ultramicrotome EM UC7" (Leica Microsystems) was used to prepare the section. The remaining block from which the uniform, hole-free section was cut was used as the measurement sample. Next, a Berkovich indenter (triangular pyramid, TI-0039 manufactured by BRUKER) was pressed vertically into the cross section of the hard coat layer under the following measurement conditions for 25 seconds until a maximum indentation load of 500 μN was reached. Here, in the optical films according to Examples 1 to 7, 9, and 10 and Comparative Examples 1 to 3, the Berkovich indenter was pressed into a portion of the hard coat layer 500 nm away from the interface between the polyimide substrate and the hard coat layer toward the center of the hard coat layer, 500 nm away from the interface between the hard coat layer and the inorganic layer toward the center of the hard coat layer, and 500 nm away from each of the two ends of the hard coat layer toward the center of the hard coat layer, in order to avoid the influence of the polyimide substrate and the inorganic layer and the side edges of the hard coat layer. For the same reason, in the optical film according to Example 8, the Berkovich indenter was pressed into a portion of the hard coat layer 500 nm away from the interface between the optical adjustment layer and the hard coat layer toward the center of the hard coat layer, 500 nm away from the interface between the hard coat layer and the inorganic layer toward the center of the hard coat layer, and 500 nm away from each of the two ends of the hard coat layer toward the center of the hard coat layer. Thereafter, the indenter was held for a certain period of time to relax the residual stress, and then unloaded over 25 seconds. The maximum load after relaxation was measured, and this maximum load P max (μN) and contact projection area A p (nm 2 ) and P max / A pThe indentation hardness was calculated by the following method. The contact projected area was the contact projected area corrected for the indenter tip curvature by the Oliver-Pharr method using a standard sample of fused quartz (5-0098 manufactured by BRUKER). Indentation hardness (H IT ) is the arithmetic mean value of the values ​​obtained by measuring at 10 locations. If the measured values ​​include any that deviate from the arithmetic mean value by more than ±20%, those measured values ​​shall be excluded and remeasured. (Measurement conditions) ·Loading speed: 20μN / sec ·Holding time: 5 seconds ·Loading and unloading speed: 20μN / sec ·Measurement temperature: 25℃

[0219] <Confirmation of the presence of metallic and semi-metallic elements and measurement of the atomic ratio of the total amount of these elements> The presence of at least one of a metal element and a metalloid element in the hard coat layer of the optical film according to the examples and comparative examples was confirmed. Specifically, first, an optical film cut into a size of 1 mm × 6 mm was cut parallel to the plane by approximately 200 nm using a microtome (product name "Ultramicrotome EM UC7" manufactured by Leica Microsystems) to expose the hard coat layer. Then, an X-ray photoelectron spectrometer (ESCA, product name "KRATOS Nova" manufactured by Shimadzu Corporation) was used to perform elemental analysis of the surface obtained by the cutting to confirm whether at least one of a metal element and a metalloid element was present. Furthermore, the atomic ratio (%) of the total amount of the metal element and the metalloid element was measured for the surface obtained by the cutting using the X-ray photoelectron spectrometer (ESCA, product name "KRATOS Nova" manufactured by Shimadzu Corporation). (Measurement conditions) Measurement method: Wide / Narrow X-ray source: Monochrome AlKα X-ray output: 150W Emission current: 10mA Acceleration voltage: 15kV Charge neutralization mechanism: ON ·Measurement area: 300×700μm Pass Energy (Survey): 160 eV Pass Energy (Narrow): 40 eV

[0220] <Area ratio of silica particles> In the cross section of the hard coat layer of the optical films according to the examples and comparative examples in the thickness direction, the area ratio of inorganic particles was determined in the region near the interface from the interface between the hard coat layer and the inorganic layer to a depth of 500 nm in the hard coat layer. The area ratio of inorganic particles in the region near the interface was determined as follows. First, a 1 mm × 10 mm optical film was cut out and embedded in an embedding resin to prepare a block. Ten uniform, hole-free sections with a thickness of 70 nm to 100 nm were cut from this block using a standard sectioning method. An "Ultramicrotome EM UC7" (Leica Microsystems) was used to prepare the sections. These 10 uniform, hole-free sections were used as measurement samples. Next, cross-sectional photographs of each measurement sample were taken using a scanning transmission electron microscope (STEM) (product name "S-4800" manufactured by Hitachi High-Technologies Corporation). Note that cross-sectional photographs were taken at one location per measurement sample. When taking these cross-sectional photographs, the detector was set to "TE," the acceleration voltage to "30 kV," and the emission current to "10 μA." The magnification was adjusted appropriately from 5,000x to 200,000x while adjusting the focus and observing whether the individual layers could be distinguished. Furthermore, when taking the cross-sectional photographs, the aperture was set to "Beam Monitor Stop 3," the objective lens stop to "3," and the WD to "8 mm." The area of ​​the 10 cross-sectional photographs obtained was set to 100%, and the ratio of the area of ​​inorganic particles to the area of ​​the interfacial region (area ratio) was calculated. The area ratio of inorganic particles in the interfacial region was calculated as the arithmetic mean value of the area ratio of inorganic particles calculated from the 10 cross-sectional photographs of the interfacial region.

[0221] <Scratch resistance> The surfaces (surfaces of the inorganic layer) of the optical films according to the examples and comparative examples were subjected to a steel wool test and evaluated. Specifically, the optical film cut into a size of 50 mm x 100 mm was fixed on a glass plate with Cellotape (registered trademark) manufactured by Nichiban Co., Ltd. so that the inorganic layer was facing up, without any folds or wrinkles. In this state, #0000 steel wool (product name "BON STAR", manufactured by Nippon Steel Wool Co., Ltd.) was used to apply 1 kg / cm 2 A steel wool test was carried out in which the optical film was rubbed 10 times back and forth at a speed of 50 mm / sec while applying a load of 1000 kJ / s, and thereafter the surface of the optical film was visually inspected for the presence or absence of scratches. The evaluation criteria were as follows: ◯: No scratches or abrasions were observed, or some scratches or abrasions were observed but at a level that did not pose a problem in practical use. ×: Scratches and scrapes were clearly observed.

[0222] <Haze measurement> The haze values ​​(total haze values) of the optical films according to the examples and comparative examples were measured. The haze values ​​were measured using a haze meter (product name "HM-150", manufactured by Murakami Color Research Laboratory) in accordance with JIS K7136:2000. The haze values ​​were measured three times for each optical film, with the film cut to a size of 50 mm x 100 mm, and placed with the inorganic layer facing away from the light source in a state free of curls, wrinkles, fingerprints, dust, etc. The arithmetic mean value of the three measurements was calculated.

[0223] <Total light transmittance> The total light transmittance of the optical films according to the examples and comparative examples was measured. The total light transmittance was measured using a haze meter (product name "HM-150", manufactured by Murakami Color Research Laboratory) in accordance with JIS K7361-1:1997. The total light transmittance was measured three times for each optical film, after cutting out a piece of 50 mm x 100 mm, with no curls or wrinkles, no fingerprints or dust, and placed with the inorganic layer side facing away from the light source. The arithmetic mean value of the three measurements was calculated.

[0224] <Foldability> The optical films according to the examples and comparative examples were subjected to a folding test to evaluate their foldability. Specifically, the optical film cut into a size of 30 mm × 100 mm was first fixed at the short sides of the optical film with fixing parts and attached to a durability tester (product name "DLDMLH-FS", manufactured by Yuasa System Equipment Co., Ltd.) so that the minimum distance between the two opposing sides was 6 mm as shown in Fig. 3(C), and a folding test was performed in which the front side of the optical film was folded 100,000 times at a 180° angle (a test in which the inorganic layer was folded on the inside and the polyimide-based substrate was folded on the outside), and the occurrence of cracks or breaks in the bent parts was examined. Similarly, a new optical film cut to a size of 30 mm x 100 mm was placed in a durability testing machine (product name "DLDMLH-FS", manufactured by Yuasa System Co., Ltd.) with the short sides of the optical film fixed to the fixing parts and the minimum distance between the two opposing sides being 2 mm, and a folding test was performed in which the front side of the optical film was folded 100,000 times at a 180° angle (a test in which the inorganic layer was on the inside and the polyimide base material was on the outside), and the bent parts were checked for cracks or breaks. The evaluation criteria were as follows: (foldability) ○: No cracks or breaks occurred at the bent portion in the folding test. ×: Cracks or breaks occurred at the bent portion during the folding test.

[0225] <Interference fringe evaluation> The optical films according to the examples and comparative examples were evaluated for the presence or absence of interference fringes. Specifically, a black acrylic plate to prevent backside reflection was attached to the backside of an optical film cut into a size of 50 mm x 100 mm via a 25 μm-thick transparent adhesive (product name "Highly Transparent Double-Sided Tape 8146-1", manufactured by 3M). Light was irradiated onto each optical film from the front side, and the optical film was visually observed for the presence or absence of interference fringes. A three-wavelength fluorescent lamp was used as the light source. The occurrence of interference fringes was evaluated according to the following criteria. ○: No interference fringes were observed. △: A small amount of interference fringes was observed. ×: Interference fringes were clearly observed.

[0226] [Table 1]

[0227] [Table 2]

[0228] The results are described below. As shown in Table 1, the hard coat layer of the optical film according to Comparative Example 1 did not contain inorganic particles or at least one of a metal element and a metalloid element, and therefore the scratch resistance of the inorganic layer surface was poor. The optical film according to Comparative Example 2 had an indentation hardness of less than 200 MPa, and therefore the scratch resistance of the inorganic layer surface was poor. The optical film according to Comparative Example 3 had a small hard coat layer thickness, and therefore the scratch resistance of the inorganic layer surface was poor. In contrast, the optical films according to Examples 1 to 10 had hard coat layers containing inorganic particles or at least one of a metal element and a metalloid element, had indentation hardnesses of 200 MPa or more, and had hard coat layer thicknesses of 2 μm or more, and therefore were excellent in scratch resistance of the inorganic layer surface. For the optical films of Examples 1 to 6 and 8 to 10, a steel wool test was conducted under the same conditions as above after the folding test, and the surfaces of the optical films were then visually inspected for scratches or abrasions. As a result, no scratches or abrasions were found on any of the optical films, or slight scratches or abrasions were found but at a level that was not problematic for practical use.

[0229] The optical films according to Examples 1 to 6 and 8 to 10 had hard coat layers with thicknesses of 10 μm or less, and therefore had better foldability than the optical film according to Example 7, in which the hard coat layer had a thickness of 20 μm.

[0230] No interference fringes were observed in the optical film of Example 7 because the hard coat layer was quite thick, in the optical film of Example 8 because an optical adjustment layer was formed, and in the optical film of Example 9 because the refractive index of the polyimide-based substrate was low.

[0231] In the optical films according to the examples, the presence of silicon in the inorganic layer was confirmed using an X-ray photoelectron spectrometer (product name "KRATOS Nova", manufactured by Shimadzu Corporation), and it was confirmed that silicon was present in the inorganic layer in all optical films. To confirm the presence of silicon in the inorganic layer, elemental analysis was performed on the surface of the inorganic layer of an optical film cut into a size of 1 mm x 6 mm using an X-ray photoelectron spectrometer (product name "KRATOS Nova", manufactured by Shimadzu Corporation) under the same measurement conditions as for the presence of metal elements and metalloid elements in the hard coat layer. [Explanation of symbols]

[0232] 10, 50...Optical film 11...Light-transmitting base material 12, 51...Hard coat layer 12A...binder resin 12B…Inorganic particles 13...Inorganic layer 40, 60...Image display device 43...Display panel 51A...Silicone resin 51B…Inorganic particles

Claims

1. An optical film comprising a light-transmitting substrate, a hard coat layer, and an inorganic layer in this order, the light-transmitting substrate contains a polyimide-based resin, a polyamideimide-based resin, a polyamide-based resin, a polyester-based resin, or a mixture thereof; the hard coat layer is in contact with the inorganic layer, the hard coat layer contains a binder resin and inorganic particles and has a single-layer structure; the thickness of the hard coat layer is 1 μm or more and 10 μm or less, the indentation hardness of the hard coat layer is 200 MPa or more and 1100 MPa or less; an optical adjustment layer provided between the light-transmitting substrate and the hard coat layer and having a film thickness of 30 nm or more and 200 nm or less; the refractive index of the optical adjustment layer is lower than the refractive index of the light-transmitting substrate and higher than the refractive index of the hard coat layer; In a cross section of the hard coat layer in the thickness direction, the area ratio of the inorganic particles in a region from the interface between the hard coat layer and the inorganic layer to a depth of 500 nm in the hard coat layer is 5% or more and 75% or less, The optical film, wherein the inorganic layer comprises silicon.

2. The optical film according to claim 1 , wherein the inorganic particles are silica particles.

3. An optical film comprising a light-transmitting substrate, a hard coat layer, and an inorganic layer in this order, the light-transmitting substrate contains a polyimide-based resin, a polyamideimide-based resin, a polyamide-based resin, a polyester-based resin, or a mixture thereof; the hard coat layer is in contact with the inorganic layer, the hard coat layer contains at least one of a metal element and a metalloid element and has a single layer structure; the thickness of the hard coat layer is 1 μm or more and 10 μm or less, the indentation hardness of the hard coat layer is 200 MPa or more and 1100 MPa or less; an optical adjustment layer provided between the light-transmitting substrate and the hard coat layer and having a film thickness of 30 nm or more and 200 nm or less; the refractive index of the optical adjustment layer is lower than the refractive index of the light-transmitting substrate and higher than the refractive index of the hard coat layer; the total atomic ratio of the metal element and the metalloid element contained in the hard coat layer, as measured by X-ray photoelectron spectroscopy, is 1.5% or more and 30% or less; The optical film, wherein the inorganic layer comprises silicon.

4. The optical film according to claim 1 , wherein the inorganic layer has a thickness of 10 nm or more and 300 nm or less.

5. The optical film according to claim 3 , wherein the hard coat layer contains a metalloid element, and the metalloid element is silicon.

6. The optical film according to claim 1 , wherein the hard coat layer comprises a polymer of a polymerizable compound containing silsesquioxane having a polymerizable functional group.

7. 7. The optical film according to claim 1, which does not crack or break when a test in which the optical film is folded 180° so that the distance between opposing sides of the optical film is 6 mm is repeated 100,000 times.

8. 8. The optical film according to claim 1, wherein the optical film does not crack or break when a test of folding the optical film 180° with the inorganic layer facing inward and with the distance between opposing sides of the optical film being 2 mm is repeated 100,000 times.

9. 9. The optical film according to claim 1, wherein the light-transmitting substrate is a substrate made of a polyimide resin, a polyamide resin, or a mixture thereof.

10. A display panel; the optical film according to claim 1 , which is disposed closer to a viewer than the display panel; The image display device, wherein the hard coat layer of the optical film is located closer to a viewer than the light-transmitting substrate.

11. The image display device according to claim 10, wherein the display panel is an organic light-emitting diode panel.

Images