Functional film, polarizing plate, and image display device

Abstract

To provide a functional film capable of achieving both adhesion between a hard coat layer and a functional layer and desired optical characteristics, and a polarizing plate and an image display device including the functional film.SOLUTION: According to one aspect of the present invention, there is provided a functional film 10 including a hard coat layer 12 containing a binder resin 13 and a plurality of inorganic particles 14, and a functional layer 16 in close contact with a surface 12A of the hard coat layer 12, wherein the hard coat layer 12 has a layered region having a density of the inorganic particles 14 of 60% or more in a first region R1 from the surface 12A of the hard coat layer 12 to a depth of 100 nm, and the density of the inorganic particles 14 in a second region R2 exceeding 100 nm from the surface 12A of the hard coat layer 12 is 59% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a functional film, a polarizing plate, and an image display device. [Background technology]

[0002] The image display surface of an image display device such as a liquid crystal display is usually coated with a protective film to prevent scratches and reflect external light. A functional film is provided to prevent this. The hard coat layer and the film have a desired function such as anti-reflection. Some have a layer in this order (see Patent Documents 1 to 3).

[0003] The hard coat layer contains inorganic particles for various reasons, such as adjusting optical properties and ensuring pencil hardness. Among inorganic particles, silica particles in particular have uniform size and can be used for various purposes. It is widely used as a functional layer due to the wide variety of variations that can be achieved. or an organic layer containing a resin formed by a sputtering method, a CVD method, or the like. Inorganic layers are used. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 4913627 [Patent Document 2] Patent No. 5700903 [Patent Document 3] Patent No. 6054019 Summary of the Invention [Problem to be solved by the invention]

[0005] In a functional film having a functional layer on a hard coat layer, the hard coat layer and the functional layer When the functional layer is an organic layer, the organic layer has a different function from the hard coat layer. In order to achieve this, the hard coat layer has a different resin composition and contents from the hard coat layer. When an organic layer is formed on the cured hard coat layer, the hard coat layer is hardened. In addition, when the functional layer is an inorganic layer, it is difficult to adhere the hard coat layer to the inorganic layer. The interface with the inorganic layer is a heterogeneous interface (organic / inorganic interface), so compared to when the functional layer is an organic layer, All of these are prone to interfacial peeling.

[0006] On the other hand, image display devices have expanded beyond televisions, which have traditionally been used mainly indoors, to include outdoor displays. Mobile devices, including mobile phones, may be used in harsher environments. Applications are expanding to include automotive applications, and the required durability and reliability are becoming more advanced. Under such circumstances, Patent Documents 1 to 3 describe the composition of the hard coat layer. However, there is no description about the interface between the hard coat layer and the functional layer, and there is no information about good adhesion between the hard coat layer and the functional layer. Furthermore, when trying to improve adhesion, it is uncertain whether the adhesiveness can be obtained. Since there is a risk that the desired optical properties may not be obtained as a hard coat layer, the adhesiveness and optical properties It is extremely difficult to achieve both of these. The desired optical properties depend on the application and installation of the functional film. Varies depending on location etc.

[0007] The present invention has been made to solve the above problems. A functional film capable of achieving both adhesion between functional layers and desired optical properties, and The present invention aims to provide a polarizing plate and an image display device having the hard coat layer. When a functional layer is formed on the surface, adhesion between the hard coat layer and the functional layer and desired optical properties are achieved. and a polarizing plate and an image display device including the hard-coated film. The purpose is to provide a place [Means for solving the problem]

[0008] According to one aspect of the present invention, a hard coat layer including a binder resin and a plurality of inorganic particles is provided. and a functional layer in close contact with the surface of the hard coat layer, The hard coat layer has a first region extending from the surface of the hard coat layer to a depth of 100 nm. the inorganic particles have a layered region in which the density of the inorganic particles is 60% or more; The density of the inorganic particles in a second region that is more than 100 nm deep from the surface is 59% or less. A functional film is provided.

[0009] In the functional film, at least a part of the inorganic particles is in contact with the hard coat layer. The inorganic particles may be present at the interface of the functional layer, and may be in close contact with the functional layer.

[0010] In the functional film, the hard coat layer contains the inorganic particles in the first region. The density of the inorganic particles in the second region is 70% or more. It may be 50% or less.

[0011] In the functional film, the maximum aggregation degree of the inorganic particles in the second region is It may be 30% or less.

[0012] In the functional film, the hard coat layer may have a thickness of 1 μm or more. stomach.

[0013] In the functional film, the hard coat layer is provided on the side opposite to the functional layer. The optically transparent substrate may further be provided.

[0014] According to another aspect of the present invention, the functional film and the hard film of the functional film a polarizer provided on the opposite side of the coating layer from the functional layer side. It is served.

[0015] According to another aspect of the present invention, a hard coat layer comprising a binder resin and a plurality of inorganic particles is provided. The hard coat film has at least the following: The hard coat layer forms the surface of the hard coat film, and the hard coat layer A portion in which the density of the inorganic particles is 60% or more within a first region from the surface to a depth of 100 nm and the second region of the hard coat layer having a depth of more than 100 nm from the surface of the hard coat layer. A hard coat film is provided in which the density of inorganic particles is 59% or less.

[0016] In the hard coat film, the inorganic particles contain Si elements, The silicon layer has a first layered region in the first region, the first layered region having a total element ratio of Si and O of 60% or more. and a second layered region in which the sum of the element ratios of Si and O is less than 60%.

[0017] In the hard coat film, the hard coat layer has the following in the first region: The inorganic particles have a part where the density of the inorganic particles is 70% or more, and the density of the inorganic particles in the second region is The density may be 50% or less.

[0018] In the hard coat film, the maximum aggregation of the inorganic particles in the second region The degree may be 30% or less.

[0019] In the above hard coat film, the thickness of the hard coat layer is 1 μm or more. That's fine.

[0020] In the hard coat film, the side opposite to the surface of the hard coat layer The optical element may further include a light-transmitting substrate provided on the rear surface side of the optical element.

[0021] According to another aspect of the present invention, the hard coat film and the hard coat film and a polarizer provided on one surface of the polarizing plate.

[0022] According to another aspect of the present invention, there is provided a method for manufacturing the functional film, the polarizing plate, or the hard coat. An image display device is provided that includes a light-emitting film. [Effects of the Invention]

[0023] According to one aspect of the present invention, adhesion between the hard coat layer and the functional layer and desired optical properties can be achieved. According to another aspect of the present invention, a functional film can be provided that can achieve both of the above characteristics. In this case, when a functional layer is formed on the surface of the hard coat layer, the density between the hard coat layer and the functional layer is It is possible to provide a hard coat film that can achieve both adhesion and optical properties. According to another aspect of the present invention, such a functional film or hard coat film It is possible to provide a polarizing plate and an image display device including the polarizing plate. [Brief explanation of the drawings]

[0024] [Figure 1] 1 is a schematic diagram illustrating a functional film according to an embodiment of the present invention. [Figure 2] FIG. 2 is an enlarged view of a portion of the functional film shown in FIG. [Figure 3]FIG. 10 is a schematic diagram of another functional film according to an embodiment. [Figure 4] 1 is a schematic diagram illustrating a polarizing plate according to an embodiment of the present invention. [Figure 5] 1 is a schematic configuration diagram of an image display device according to an embodiment. [Figure 6] 1 is a scanning transmission electron microscope photograph of a cross section of a hard coat layer in a functional film according to Example 1. [Figure 7] 1 is an image of the functional film according to Example 1 after being binarized by spreadsheet software. DETAILED DESCRIPTION OF THE INVENTION

[0025] Hereinafter, the functional film, polarizing plate, and image display device according to the embodiments of the present invention will be described. The following description will be made with reference to the drawings. In this specification, the terms "film", "sheet", etc. , are not distinguished from one another solely on the basis of differences in name. The term "film" is used to include a member also called a sheet. 2 is a schematic diagram of a functional film according to an embodiment of the present invention; FIG. 3 is a schematic diagram of a functional film according to an embodiment of the present invention; FIG. 3 is an enlarged view of a portion of the functional film according to the present embodiment, and FIG. 4 is a schematic diagram of another functional film according to the present embodiment. 4 is a schematic diagram of a polarizing plate according to this embodiment, and FIG. 5 is an image display device according to this embodiment. FIG.

[0026] <<<Functional films and hard-coated films>>> The functional film 10 shown in FIG. 1 comprises a light-transmitting substrate 11, a binder resin 13, and a hard coat film (15) having a hard coat layer (12) containing a plurality of inorganic particles (14); The surface 15A of the hard coat film 15 (the surface 12A of the hard coat layer 12) is adhered to the surface 15A. The functional film 10 and the hard coat film 15 are provided in this order. Although the light-transmitting substrate 11 is provided, it is not necessary to provide a light-transmitting substrate as will be described later. In addition, functional films and hard-coated films are made of a light-transmitting substrate and a hard-coated layer. In order to improve adhesion, a resin-containing underlayer is placed between the light-transmitting substrate and the hard coat layer. It may further comprise:

[0027] The functional film 10 and hard coat film 15 have different properties depending on the application. When used to transmit light and anti-glare properties are required, In cases where the haze value (total haze value) is not sufficient, it is generally preferable that the haze value be 1.0% or less. At this time, the haze value of the functional film 10 and the hard coat film 15 is 1.0% or less. In this case, the functional film 10 and the hard coat film 11 can have excellent transparency. The haze value of the heat film 15 is more preferably 0.9% or less, and more preferably 0.8% or less. On the other hand, when antiglare property is required, it is most preferable that the antiglare property and the haze value are The required value varies depending on the balance. Specifically, for example, the haze value should be between 2% and 45%. The 60° gloss value is often designed to be in the range of 20% to 130%. It is known that a higher haze value tends to have better anti-glare properties, but simply having a high haze value is not enough. This does not mean that it is simply desirable as an anti-glare film, but rather that it is also desirable as a functional film or hard film. The target value varies depending on the application of the coated film, the installation location, etc., so it is not possible to determine the optimum range. It is difficult to do so.

[0028] The above haze values ​​were measured using a haze meter (product name "HM-150", manufactured by Murakami Color Research Institute Co., Ltd.). Measurements can be performed using a method conforming to JIS K7136:2000 using a fluororesin (manufactured by the Institute of Chemical Research). The above haze value is measured after cutting the functional film into a size of 50 mm x 50 mm. The product must be installed without curls or wrinkles, and without fingerprints or dust. The measurement is carried out three times for one film, and the arithmetic mean value of the three measurements is used. In the book, "measure three times" does not mean measuring the same place three times, but three different places. This means measuring the functional film 10 and the hard coat film 15. In this case, the surface 10A is flat when viewed with the naked eye, and the laminated layers such as the hard coat layer 12 are also flat. The film is flat and the film thickness variation is within the range of ±10%. By measuring the haze value at three different points on the functional film, the approximate functional film It is thought that the average haze value of the entire surface of the hard coat film can be obtained. The variation in values ​​was small even when the measurement target was as long as 1m x 3000m, using a 5-inch smartphone. Even if the size is about the same as a phone, the error is within ±10%. For example, if the inlet opening of the HM-150 is 20 mm in diameter, Therefore, a sample size of 21 mm or more in diameter is required. Cut the functional film or hard coat film into a size of 22 mm or more. If the size of the functional film or hard coat film is small, the light source spot Shift the sensor little by little as long as it does not come off, or change the angle to make three measurement points.

[0029] A functional layer film or hard coat film is attached to other films such as a polarizing plate via an adhesive layer or bonding layer. If a film is provided, peel off the other film along with the adhesive layer and adhesive layer, and then The haze value is measured after thoroughly wiping off any dirt on the adhesive layer or the adhesive layer with alcohol. The other film can be peeled off, for example, as follows. A laminated film with other films attached via an adhesive layer or bonding layer to a functional film or hard coated film. The layered body is heated with a dryer to separate the boundary between the functional film or hard coat film and other films. Insert the tip of the cutter into the area that you think is the surface and slowly peel it off. By repeating this process, the adhesive layer, the bonding layer, and other films can be peeled off. Even if such a peeling step is performed, it does not have a significant effect on the measurement of the haze value.

[0030] The above 60° gloss values ​​were measured using a precision gloss meter (product name "GM-26D", Murakami Color Technology Co., Ltd. Measurement should be performed using a test kit manufactured by the Institute, using a method conforming to JIS Z8741:1997. The above 60° gloss values ​​are obtained by measuring functional films and hard-coated films 50mm x 100mm. After cutting into 50mm pieces, the backside of the functional film or hard coat film is air-coated. The measurement is performed by attaching the material to a non-glossy black resin plate using the suction method and then placing it on a precision gloss meter. The above 60° gloss value is for one sheet of functional film or hard coat film. The measurement is carried out three times and the arithmetic mean value obtained from the three measurements is used.

[0031] In the functional film 10 and the hard coat film 15, the total light transmittance is 85%. The total light transmittance of the functional film 10 and the hard coat film 15 is preferably equal to or greater than 100%. If the transmittance is 80% or more, sufficient light transmittance can be obtained. The total light transmittance is more preferably 88% or more, and most preferably 90% or more. I wish.

[0032] The total light transmittance was measured using a haze meter (product name "HM-150" manufactured by Murakami Color Technology Co., Ltd.). Measurement is performed using a method conforming to JIS K7361-1:1997 using a fluororesin (manufactured by the Institute of Chemical Research). The total light transmittance mentioned above is the same as that of functional films and hard-coated films at 50 mm. After cutting it into a size of 50 x 50 mm, set it in a state that there are no curls or wrinkles, and that there is no fingerprints or dust. The functional film or hard coat film was placed in the position and measured three times. In the case of the functional film 10 or the hard coat film, The surface 10A is flat when visually observed, and the layers to be laminated, such as the hard coat layer 12, are also flat. The film thickness variation is also within the range of ±10%. By measuring the total light transmittance at three different points on the film, it is possible to roughly estimate the It is thought that the average value of the total light transmittance of the entire surface of the coated film can be obtained. The variation in transmittance is as small as 1m x 3000m, even with a 5-inch smart Even for a size of about a phone, the error is within ±10%. If you cannot cut the film to the above dimensions, cut it to a size of 22mm x 22mm or larger. The functional film may be cut out appropriately. If the distance is small, move it little by little or change the angle within the range that the light spot remains. In this way, there are three measurement points.

[0033] In addition, functional films and hard coat films can be coated with adhesive layers to form polarizing plates and other products. If a film is provided, the adhesive layer and the adhesive layer are removed in the same manner as above. After peeling off the other film, measure the total light transmittance of the functional film. Even if such a peeling step is performed, it does not have a significant effect on the measurement of total light transmittance.

[0034] The surface 10A of the functional film 10 (the surface of the functional layer 16) and the hard coat film 15 Surface 15A is measured using the pencil hardness test specified in JIS K5600-5-4:1999 The hardness (pencil hardness) when the adhesive is applied is preferably B or higher, more preferably H or higher. The pencil hardness test is carried out on a functional film cut to a size of 50 mm x 50 mm. Apply the hard coat film or the cellophane made by Nichiban Co., Ltd. to the glass plate without any creases or folds. The pencil was fixed with tape (registered trademark), and a load of 1 kg was applied to the pencil while the scratching speed was 1 The pencil hardness test is carried out at a speed of mm / sec. The hardness is the highest level that does not scratch the surface of the hard coat film or hard-coated film. When measuring the hardness, several pencils with different hardness are used, and each pencil is tested five times for pencil hardness. The surface of functional film or hard coat film was scratched in more than four out of five tests. If it does not stick, then it is recommended to use a functional film or hard coat film for pencils of this hardness. The above scratches were not found on the surface of the functional film that was subjected to the pencil hardness test. This refers to what can be seen when observing the surface of a hard coat film or hard coat film under fluorescent light.

[0035] The functional film 10 and the hard coat film 15 may be used for various purposes, including, but not limited to, optical applications. When it functions as a film, it is used for the functional film 10 or the hard coat film 15. For example, personal computers including notebook personal computers ( PC), smartphones, tablets, wearable devices, digital signage, Examples include image display devices such as revisions and car navigation systems. Functional films 10 may also be used as a packaging material.

[0036] The functional film 10 and the hard coat film 15 are cut to a desired size. The functional film 10 and the hard coat film 15 may be in a roll shape. When cut to the desired size, the size of functional film or hard coat film is not particularly limited, and the application (for example, when used in an image display device, Specifically, the functional film 10 and the hard The size of the coated film 15 is, for example, 2.8 inches or more and 500 inches or less. In this specification, the term "inch" refers to the thickness of a functional film or a hard coat film. In the case of a square, it means the length of the diagonal line, in the case of a circle, it means the diameter, and in the case of an ellipse, it means the length of the diagonal line. In the case of a circular shape, the average value of the sum of the short diameter and the long diameter is used. If the film or hard coat film is rectangular, the functionality when calculating the above inches is The aspect ratio of the film is not particularly limited as long as it does not cause any problems when used as a display screen for an image display device. For example, the ratio of vertical to horizontal is 1:1, 4:3, 16:10, 16:9, 2:1, etc. However, in particular, in the case of in-vehicle applications and digital signage, which require sophisticated design, such vertical and horizontal The ratio is not limited to the above. If the size is too large, cut it out from any position to A5 size (148mm x 210mm), The data shall be cut to the size of each measurement item.

[0037] <<Light transparent base material>> The light-transmitting substrate 11 is not particularly limited as long as it is a substrate having light-transmitting properties. For example, Ester-based base material, acetyl cellulose-based base material, cycloolefin polymer base material, polyethylene Tersulfone-based substrates, polycarbonate-based substrates, polyamide-based substrates, polyimide-based substrates, Polyolefin-based substrate, acrylic-based substrate, polyvinyl chloride-based substrate, polyvinylidene chloride-based substrate Substrate, polystyrene substrate, polyvinyl alcohol substrate, polyarylate substrate, poly Among these, the most popular are those that suppress interference fringes caused by birefringence. From the viewpoint of adhesion to the control and hard coat layer, acetyl cellulose-based substrates and acrylic-based The light-transmitting substrate 11 may contain additives and the like in addition to the resin.

[0038] Examples of polyester-based substrates include polyethylene terephthalate (PET), poly Propylene terephthalate (PEN), polybutylene terephthalate, polyethylene naphtha Examples of the base material include a base material containing at least one kind of talc as a constituent component.

[0039] Examples of acetyl cellulose-based substrates include triacetyl cellulose-based substrates and diacetyl cellulose-based substrates. Triacetyl cellulose-based substrates are suitable for use in the visible light range of 380°C. It is a substrate that can achieve an average light transmittance of 50% or more at wavelengths up to 780 nm. The average light transmittance of the acetyl cellulose base material is preferably 70% or more, and more preferably 85% or more. I wish.

[0040] In addition to pure triacetyl cellulose, triacetyl cellulose-based base materials include cellulose acetate propionate, cellulose acetate butyrate, etc. The fatty acid that forms the ester with the base may contain a component other than acetic acid. In addition, these triacetyl celluloses may be mixed with other compounds such as diacetyl cellulose, if necessary. A cellulose lower fatty acid ester may also be added.

[0041] Examples of cycloolefin polymer-based substrates include norbornene-based monomers and monocyclic Examples of the substrate include a polymer of a cycloolefin monomer. Commercially available products of mer include Zeonex and Zeonor (Norborne) manufactured by Zeon Corporation. resin), Sumilite FS-1700 manufactured by Sumitomo Bakelite Co., Ltd., Arton manufactured by JSR Corporation (modified norbornene resin), Apel (cyclic olefin copolymer) manufactured by Mitsui Chemicals, Ti Topas (cyclic olefin copolymer) manufactured by Cona, Optretz O manufactured by Hitachi Chemical Z-1000 series (alicyclic acrylic resin) and the like.

[0042] Examples of polycarbonate substrates include bisphenols (such as bisphenol A). Aromatic polycarbonate substrate based on diethylene glycol bisallyl carbonate Examples of the base material include aliphatic polycarbonate substrates such as polyethylene terephthalate.

[0043] Examples of acrylic substrates include (meth)acrylic esters, acrylamides, and Obtained by polymerizing monomers such as acrylic acid, (meth)acrylic acid, or their derivatives Among these, from the viewpoint of transparency and weather resistance, a substrate made of a resin is preferred. Methyl methacrylate (PMMA), a copolymer whose main component is methyl methacrylate units and styrene-methyl methacrylate copolymers are preferred.

[0044] The thickness of the light-transmitting substrate 11 is preferably 20 μm or more and 200 μm or less. If the thickness of the transparent substrate 11 is 20 μm or more, wrinkles will not occur and the transparent substrate 11 will have excellent pencil hardness. A functional film having a high optical transparency can be obtained, and the thickness of the light-transmitting substrate 11 can be reduced to 200 μm. If the thickness is less than 1 / 2 inch, the flexibility is such that it can be handled in a roll. The cross section of the light-transmitting substrate is photographed using a scanning electron microscope (SEM), and the image of the cross section is The thickness of the light-transmitting substrate was measured at 20 points in the image, and the arithmetic mean value of the thickness at those 20 points was calculated. This can be found by

[0045] <<Hard Coat Layer>> In the hard coat film 15, the surface 12A of the hard coat layer 12 is a hard coat. The hard coat layer 12 is a surface 15A of the hard coat film 15. and a plurality of inorganic particles 14. The hard coat layer 12 includes a binder resin 13 and inorganic particles 14. In addition to D14, it contains ingredients such as UV absorbers, leveling agents, and silane coupling agents. Good too.

[0046] The hard coat layer 12 has a single layer structure, but may have a multi-layer structure of two or more layers. In this specification, the term "hard coat layer" refers to a layer that has optical transparency and a Martens hardness of 1. In this specification, the term "Martens hardness" means a layer having a hardness of 0.00 MPa or more. The hardness was measured by nanoindentation method, and the hardness was measured when the indenter was pressed 500 nm. The Martens hardness was measured by the nanoindentation method. HYSITRON's TI950 TriboInden Specifically, first, a machine cut into 1 mm x 10 mm pieces is used. A block was prepared by embedding the functional film in an embedding resin, and a general The section preparation method is used to cut uniform sections with a thickness of 70 nm to 100 nm, without holes. To prepare the sections, an ultramicrotome EM UC7 (Leica Microsystems) was used. (Thames Corporation) can be used. Then, uniform slices without holes etc. are cut out. The remaining blocks are used as measurement samples. In the cross section obtained by cutting out the slice, the pressure was measured under the following measurement conditions. The Berkovich indenter (triangular pyramid) was pressed 500 nm into the center of the cross section of the hard coat layer. After the residual stress is relaxed by holding the load constant, the load is removed and the maximum load after relaxation is measured. Maximum load P max (μN) and the area of ​​the 500 nm deep depression A (nm 2 ) and P ma x Martens hardness is calculated by measuring at 10 points. The arithmetic mean value of the values ​​obtained shall be used. (Measurement conditions) ·Loading speed: 10nm / sec ·Holding time: 5 seconds ·Loading and unloading speed: 10nm / sec ·Measurement temperature: 25℃

[0047] The thickness of the hard coat layer 12 is preferably 1 μm or more. If the thickness of the layer 12 is 1 μm or more, sufficient hardness can be maintained. The lower limit of the thickness of the hard coat layer 12 is more preferably 2 μm or more. The upper limit of the thickness is 20 μm to prevent deterioration of processability due to excessive thickness. It is preferable that the thickness is 10 μm or less, and more preferable that the thickness is 10 μm or less.

[0048] The thickness of the hard coat layer was measured using a scanning transmission electron microscope (STEM) or a transmission electron microscope. A cross section of the hard coat layer was photographed using a transmission electron microscope (TEM), and the hard coat layer was The thickness of the coating layer is measured at 20 points, and the arithmetic mean value of the thicknesses at those 20 points is used. The method for taking surface photographs is described below. First, a functional film cut to 15 mm x 10 mm was Films and hard-coated films are fixed to a resin plate and then scanned with a Chromatome EM UC6 (Leica Model 6). After cutting to a width of 300 μm and a height of 80 μm using a trimming machine (manufactured by Microsystems Co., Ltd.), Furthermore, the DiATOME Diamond Knife ULTRA is used to cut in the thickness direction. Then, cut out uniform sections with a thickness of 70 nm to 100 nm without holes. For this purpose, we used an ultramicrotome EM UC7 (Leica Microsystems). Then, measure the remaining block from which the uniform section without holes etc. has been cut out. The measurement sample was prepared by the commonly used method of incorporating it into resin. Then, a scanning transmission electron microscope (STEM) (product name "S-4800"; stock A cross-sectional photograph of the measurement sample is taken using a microscope (manufactured by Hitachi High-Technologies Corporation). When taking cross-sectional images using the S-4800, the detector should be set to "TE" and the accelerating voltage to "5k The cross section is observed with the emission current set to 10µA and the magnification set to 10µA. Adjust the contrast and brightness to 5000~ while observing whether each layer can be distinguished. Adjust the magnification appropriately to 200,000 times. When taking cross-sectional photographs using the S-4800, Furthermore, set the aperture to "Beam monitor aperture 3" and the objective lens aperture to "3". The WD may be set to 8 mm. When measuring the thickness of the hard coat layer, When this was realized, the interface contrast between the hard coat layer and other layers (for example, the light-transmitting substrate) It is important to be able to observe as clearly as possible. If the interface is not visible due to insufficient contrast, If this is difficult, dyeing with osmium tetroxide, ruthenium tetroxide, phosphotungstic acid, etc. If the organic layer is treated with a dye, the interface between the organic layers becomes easier to see, so a dyeing treatment may be carried out. The contrast may be more difficult to see at higher magnifications. In that case, the same can be done at lower magnifications. For example, two magnifications, high and low, such as 25,000 times and 50,000 times, or 50,000 times and 100,000 times, are used. The arithmetic mean value was calculated at both magnifications, and the mean value was used to calculate the hard coat layer. This is the film thickness value.

[0049] <Binder resin> The binder resin 13 contains a polymer (cured product) of a polymerizable compound (curable compound). The polymerizable compound has at least one polymerizable functional group in the molecule and is polymerized by ionizing radiation. The compound may be either an ionizing radiation polymerizable compound that polymerizes by irradiation or a thermally polymerizable compound that polymerizes by heat. Examples of the polymerizable functional group include a (meth)acryloyl group, a vinyl group, an allyl group, etc. The term "(meth)acryloyl group" refers to an ethylenically unsaturated group. The term "methacryloyl group" includes both "acryloyl group" and "methacryloyl group." These include visible light, ultraviolet light, X-rays, electron beams, alpha rays, beta rays, and gamma rays.

[0050] The polymerizable compound may include, in addition to the first polymerizable monomer, a second polymerizable monomer, It may contain a polymerizable oligomer and / or a polymerizable prepolymer.

[0051] The second polymerizable monomer is preferably a polyfunctional (meth)acrylate. Examples of (meth)acrylates include trimethylolpropane tri(meth)acrylate. acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate Di(meth)acrylate, dipropylene glycol di(meth)acrylate, pentaerythritol Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di Pentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate ) acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane Panthenyl (meth)acrylate, ditrimethylolpropane tetra (meth)acrylate , dipentaerythritol penta(meth)acrylate, tripentaerythritol octyl (meth)acrylate, tetrapentaerythritol deca(meth)acrylate, isopropyl alcohol Cyanuric acid tri(meth)acrylate, isocyanuric acid di(meth)acrylate, polyethylene Steltri(meth)acrylate, polyester di(meth)acrylate, bisphenol Diglycerin tetra(meth)acrylate, adamantyl diacrylate (meth)acrylate, isoboronyl di(meth)acrylate, dicyclopentane di(meth)acrylate meth)acrylate, tricyclodecane di(meth)acrylate, ditrimethylolpropane Tetra(meth)acrylate and those modified with PO, EO, caprolactone, etc. Examples include:

[0052] Among these, tri- to hexafunctional ones are preferred because they can suitably satisfy the above-mentioned Martens hardness. Preferred are, for example, pentaerythritol triacrylate (PETA), dipentaerythritol triacrylate (DIA), Erythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate Dipentaerythritol pentaacrylate (PETTA), dipentaerythritol pentaacrylate (DPPA), trime Tyrolpropane tri(meth)acrylate, Tripentaerythritol octa(meth)acrylate acrylate, tetrapentaerythritol deca(meth)acrylate, and the like are preferred.

[0053] In order to adjust the hardness and viscosity of the composition, the second polymerizable monomer may be a polyfunctional monomer. In addition to the above, the copolymer may further contain a monofunctional (meth)acrylate monomer. ) Acrylate monomers include, for example, hydroxyethyl acrylate (HEA), Glycidyl methacrylate, methoxypolyethylene glycol (meth)acrylate, Sostearyl (meth)acrylate, 2-acryloyloxyethyl succinate, acrylic acid N-Acryloylmorpholine, N-Acryloyloxyethylhexahydrophthalimide, Cyclo Hexyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, Examples include phenoxyethyl acrylate and adamantyl acrylate.

[0054] As the polymerizable oligomer or polymerizable prepolymer, urethane (meth)acrylate , polyester (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate ) acrylate, polyfluoroalkyl (meth)acrylate, silicone (meth)acrylate These polymerizable oligomers or prepolymers include acrylates and the like. The polymerizable prepolymers may be used alone or in combination of two or more.

[0055] The weight average molecular weight of the first polymerizable monomer and the second polymerizable monomer is From the viewpoint of improving the hardness of the layer, it is preferably less than 1000, and more preferably 200 to 800. The weight average molecular weight of the polymerizable oligomer is preferably 1,000 or more and 20,000 or less. It is preferable that the number of carbon atoms is 1,000 or more and 10,000 or less, more preferably 2,000 or more and 70,000 or less. It is more preferable that the weight average molecular weight is 00 or less. Dissolved in a solvent such as hydrofuran (THF) and subjected to conventional gel permeation chromatography. This is a value obtained by gel permeation chromatography (GPC) method and converted into polystyrene.

[0056] The binder resin 13 preferably contains phosphorus (P). By including the element, the adhesion between the binder resin 13 and the inorganic particles 14 can be improved. Whether or not the binder resin 13 contains phosphorus can be determined by X-ray photoelectron spectroscopy (XPS). electron spectroscopy, or ESCA (Electron Spectroscopy for Chemical Analysis This can be confirmed by:

[0057] When the binder resin 13 contains phosphorus (P), the surface 12A of the hard coat layer 12 In the element ratio of the surface 12A, phosphorus is preferably 0.1% or more. If the phosphorus content is 0.1% or more, the adhesion between the hard coat layer 12 and the functional layer 16 can be further improved. The element ratios on the first surface of the hard coat layer can be measured by XPS or The lower limit of phosphorus in the above element ratio is 0.3% or more. The upper limit is the increase in haze due to aggregation of phosphorus-containing components during coating. From the viewpoint of suppression, it is preferably 10% or less.

[0058] The phosphorus element is contained in the binder resin 13 by using a phosphoric acid-based monomer. The phosphoric acid-based monomer contains a phosphoric acid group and a polymerizable functional group. Examples of the monomer include ethylene oxide-modified phosphate (meth)acrylate, Ethylene oxide modified di(meth)acrylate phosphate, dimethyl phosphate ethyl acrylate Acrylate, Diethyl Phosphate Ethyl Acrylate, 2-Acryloyloxyethyl Acrylate Phosphoric acid, bisacryloyloxyethyl phosphate, trisacryloyloxyethyl phosphate phosphate, 2-methacryloyloxyethyl phosphate, bismethacryloyloxyethyl Phosphate, ethoxylated phosphate tri(meth)acrylate. The phosphate group of the phosphate monomer interacts with the inorganic particles through hydrogen bonding, and the The polymerizable functional group bonds with the polymerizable compound to form a binder resin 13 and inorganic particles 14. Therefore, the adhesion between the hard coat layer 12 and the functional layer 16 can be improved. Peeling can be further suppressed.

[0059] <Inorganic particles> The hard coat layer 12 is formed by a first layer 12A extending from the surface 12A of the hard coat layer 12 to a depth of 100 nm. 1 (see FIG. 2), a layered region (hereinafter referred to as this region) in which the density of the inorganic particles 14 is 60% or more is formed. The region is referred to as a "high density layer region." In the second region R2 (see FIG. 2) having a depth of 100 nm or more, the density of the inorganic particles 14 is 59% or less. In this specification, the "density of inorganic particles" refers to the density of the first and second regions. In each region, the degree of density of the inorganic particles in the direction perpendicular to the thickness direction of the hard coat layer is Therefore, the dense layered region in the first region R1 is an index showing whether particles exist. The density of the inorganic particles 14 in the first region R1 is higher than the density of the inorganic particles 14 in the second region R2. This means that the inorganic particles 14 The dense layered region is more abundant in the first region R1 than in the second region R2. As will be described later, the hard coat layer is aligned in a direction perpendicular to the film thickness direction. A plurality of cells is defined as one row, and the density of inorganic particles is calculated for each row. The region where the density of the particles is 60% or more appears as a layer. From the viewpoint of achieving a higher level of adhesion between the 16 and the desired optical properties, The maximum density of the inorganic particles 14 in the dense layered region within region R1 of 1 is 70% or more. and the density of the inorganic particles 14 in the second region R2 is preferably 50% or less. .

[0060] The density of the inorganic particles in the first region can be determined by the following method. First, a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM) was used to The cross-sectional image of the hard coat layer was taken at 30,000 to 100,000 magnifications and processed using image processing software (product The images were read using the software "ImageJ" (manufactured by the National Institutes of Health, USA), and each cell was converted to black and white. In this case, it is preferable that the number of pixels for binarization processing is 640 x 480 or more. In cross-sectional EM or STEM images, dense inorganic particles are transparent to the electron beam. The binder resin, which has a lower density than the inorganic particles, appears white. Therefore, when binarization is performed, the inorganic particles appear as black areas and the binder resin appears as white areas. If the division between the white and black areas is on the white side of the average value of all cells, If it is on the resin part, or on the black side, it is considered to be a particle part. Among the cells, a number of cells aligned in a direction perpendicular to the film thickness direction of the hard coat layer are considered as one row. For each cell in a column, determine whether it is a black part or a white part. The ratio (%) of the number of cells judged as black to the total number of cells in the first region is calculated. In this case, the entire area is analyzed, and if there is a part where the density is 60% or more, it is classified as the first area. It can be determined that a dense layered region exists in the direction perpendicular to the film thickness direction. It is not necessary to analyze the entire width of the TEM or STEM image obtained, but It is sufficient to include the number of cells that can provide analytical accuracy. Specifically, if there are 100 or more cells, high accuracy will be obtained. degree is obtained.

[0061] The density of the inorganic particles in the second region is similar to the density of the inorganic particles in the first region. In the second region, at least five rows of the above are required at different depths. The inorganic particles in the second region are determined by calculating the ratio and calculating the arithmetic mean value thereof. The density is as follows.

[0062] Method for taking cross-sectional photographs of hard coat layers using STEM to determine the density of inorganic particles 14 The method of taking the cross-sectional photographs was the same as that described in the hard coat layer thickness column, except for the magnification. do.

[0063] The above binarization process was performed using image processing software (product name: ImageJ, National Institutes of Health, USA). Specifically, the following procedure is performed: First, the The image of the photograph is read and displayed in black and white on a spreadsheet software cell, with one pixel per cell. The gradation of the black and white is output as a numerical value. In this case, it is better to have as many gradations of black and white as possible. It is preferable to carry out the subsequent data analysis with 128 or more gradations. The processing does not depend on specific software, and can be calculated using a spreadsheet software macro, etc. no problem.

[0064] The inorganic particles 14 are preferably silica particles in order to obtain excellent hardness. In the case of a polymer layer, at least some of the inorganic particles 14 are hard coated, as shown in FIG. It is preferably present at the interface between layer 12 and functional layer 16 and in direct contact with functional layer 16 . The inorganic particles 14 present at the interface are directly attached to the functional layer 16, and thus the inorganic particles 14 and Since the interface between the hard coat layer 12 and the functional layer 16 is an inorganic / inorganic interface, The inorganic particles can further improve the adhesion between the hard coat layer and the functional layer. Whether or not the hard coat layer is present in the hard coat layer can be determined by examining the cross section of the hard coat layer with a scanning transmission electron microscope (STEM) or This can be confirmed by observing with a transmission electron microscope (TEM). As a method for cross-sectional analysis of the coated layer, a surface and interface cutting test device (SAICAS) was used. Diagonal cutting and cutting with a microtome can be used. The cross section of the functional film is exposed by cutting with the After being exposed to a long-term test environment using a xenon weather tester, the product is further exposed to a humid and hot environment. Alternatively, a solvent such as alcohol may be applied to the vicinity of the cross section to forcibly peel off the functional layer. After peeling off the functional layer, it was observed whether inorganic particles were present at the interface between the hard coat layer and the functional layer. You can guess.

[0065] In the hard coat layer 12, the inorganic particles 14 contain Si elements, and Si and A first layered region having an element ratio of O of 60% or more and a first layered region having an element ratio of Si and O of less than 60% in total. It is preferable that the first region R1 contains a second layered region having an element ratio of Si and O of If the first layered region has a total of 60% or more of the hard coat layer 12 and the functional layer 1, In addition, the elements Si and O are contained in the first region R1. If the total ratio of the second layered region is less than 60%, there are too many inorganic particles 14. The deterioration of optical properties due to the above can be further suppressed. The element ratio of Si and O was measured using a scanning X-ray photoelectron spectrometer (product name: Quantum2000) ) manufactured by ULVAC-PHI, Inc.) was used to measure the depth of the hard coat layer under the following measurement conditions. The thickness of the substrate was etched in the thickness direction, and the element ratios of Si and O were determined every 5 nm. It is found by: (Measurement conditions) ·X-ray conditions: Al mono 200μmφ×30W 15kV, Photoelectron capture angle: 45° Etching conditions: 2kV raster 2×2

[0066] The maximum aggregation degree of the inorganic particles 14 in the second region R2 is preferably 30% or less. If the maximum aggregation degree of the inorganic particles 14 in the second region R2 is 30% or less, the optical characteristics are The maximum aggregation degree of the inorganic particles 14 in the second region R2 is 20 % or less, and more preferably 10% or less (the smaller the value, the better). The "maximum degree of aggregation of inorganic particles in the second region" in the document refers to the cross section of the hard coat layer. When observed, the second region has a predetermined width in a direction perpendicular to the film thickness direction of the hard coat layer. The part extending from the line is considered as one row, and the number of inorganic particles in one row is three or more. The ratio of the number of inorganic particles that are adjacent to each other and form a cluster is called the aggregate of inorganic particles in a row. The degree of aggregation of the inorganic particles was determined in multiple rows (for example, any 10 to 30 rows). When the degree of aggregation is larger than the degree of aggregation of inorganic particles determined in multiple rows, it means the largest degree of aggregation of inorganic particles determined in multiple rows. The maximum aggregation degree of the inorganic particles 14 in the second region R2 is calculated as follows. Among the cells appearing in the image after binarization, the cells that are perpendicular to the film thickness direction of the hard coat layer are A row of cells is made up of cells arranged in the same direction, and the cells are continuous with a length of at least three times the primary particle size of the inorganic particles. The number of inorganic particles in a row is determined to be in an agglomerated state. The percentage of cells that are continuous with a length of at least three times the primary particle size is found, and the degree of aggregation of one row is calculated. Then, the degree of aggregation of the inorganic particles is determined for multiple rows (for example, any 10 to 30 rows). The largest aggregation degree among the inorganic particles found by the numerical sequence is taken as the maximum aggregation degree. "Diameter" refers to the smallest dimension among the diameter, width, depth, and height of multiple inorganic particles. do.

[0067] The inorganic particles may be spherical particles, but are preferably irregularly shaped particles. The irregular-shaped particles may be mixed with the spherical particles. The irregular-shaped particles have a larger surface area than the spherical particles. Therefore, by including such irregularly shaped particles, the contact area with the polymerizable compound is increased. As a result, the hardness of the hard coat layer can be improved. Whether the inorganic particles used are irregular particles or not can be determined by observing the cross section of the hard coat layer with a transmission electron microscope (T This can be confirmed by observing the structure with a scanning electron microscope (EM) or scanning transmission electron microscope (STEM). In this specification, the term "spherical particles" refers to particles such as perfect spheres and oval spheres. "irregular shaped particles" refers to potato-shaped particles (with an aspect ratio of 1.2 when observed in cross section). The term "particles" refers to particles having a shape with random irregularities on the surface (amount of irregularities is 40 or more).

[0068] The average primary particle size of the inorganic particles 14 is preferably 5 nm or more and 100 nm or less. If the average primary particle size of the inorganic particles 14 is 5 nm or more, the inorganic particles can be easily produced. In addition, if the thickness is 100 nm or less, large irregularities will not be formed on the hard coat layer 12. When inorganic particles are spherical particles, the average primary particle size of the inorganic particles can be measured by a transmission electron microscope (T Electron microscopes (EM) or scanning transmission electron microscopes (STEM) were used at magnifications of 40,000 to 200,000. The primary particle size of 20 inorganic particles was measured from the cross-sectional image of the inorganic particles. The arithmetic mean value of the primary particle diameter. If the inorganic particles are irregularly shaped, the mean value of the inorganic particles The uniform primary particle size can be determined using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM). The maximum distance between two points on the periphery of the inorganic particle ( The primary particle size of 20 inorganic particles was calculated by measuring the longest diameter and the smallest diameter. The arithmetic mean value of the particle size is used.

[0069] By controlling the size and amount of the inorganic particles 14, the hardness (martensiticity) of the hard coat layer 12 can be adjusted. For example, the inorganic particles 14 have a diameter of 5 nm or more and 100 nm or less. In this case, the content of the inorganic particles 14 is 25 parts by mass relative to 100 parts by mass of the polymerizable compound. It is preferably 60 parts by mass or more.

[0070] When silica particles are used as inorganic particles, the silica particles may be reactive silica particles. The reactive silica particles can form a crosslinked structure with the polymerizable compound. The reactive silica particles are capable of reacting with the hard coat layer 12. The hardness can be increased sufficiently.

[0071] The reactive silica particles preferably have reactive functional groups on their surfaces. As the functional group, for example, the above-mentioned polymerizable functional groups are preferably used.

[0072] The reactive silica particles are not particularly limited, and conventionally known ones can be used. For example, reactive silica particles described in JP-A-2008-165040 can be mentioned. Commercially available reactive silica particles include, for example, MIBK-SD and MIBK-SD -MS, MIBK-SD-L, MIBK-SD-ZL (all manufactured by Nissan Chemical Industries, Ltd.) Examples of suitable catalysts include V8802 and V8803 (all manufactured by JGC Catalysts and Chemicals Co., Ltd.).

[0073] The hard coat layer 12 further contains organic particles for a different purpose in addition to the inorganic particles 14. The organic particles may include polymethyl methacrylate particles, polyacrylic-styrene particles, and the like. copolymer particles, melamine resin particles, polycarbonate particles, polystyrene particles, cross-linked poly Styrene particles, polyvinyl chloride particles, benzoguanamine-melamine formaldehyde particles Examples of organic particles include silicone particles, fluorine-based resin particles, and polyester-based resin particles. The particles may be mixed with an inorganic component.

[0074] <UV absorber> The ultraviolet absorber has the function of absorbing ultraviolet rays. Although not limited, examples of ultraviolet absorbers include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers. .

[0075] 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-dodecyloxypropanol [4,6-bis(2,4-dimethylphenyl)-4,6-bis(2-hydroxy ... )-1,3,5-triazine, 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, etc. Commercially available triazine-based ultraviolet absorbers include, for example, TINUVIN46 0 and 477 (both manufactured by BASF Japan Ltd.).

[0076] <Leveling agent> The leveling agent is a compound that is produced when the surface tension of the hard coat layer 12 becomes uneven. Additives that prevent defects such as craters, dents, pinholes, and dents and smooth the surface The leveling agent is not particularly limited, but may be a polyether group, a polyurethane group, an ethylene group, epoxy group, carboxyl group, acrylate group, methacrylate group, carbinol group or water The leveling agent may be a compound having a polyether group, a polyurethane group, or the like. acrylate group, epoxy group, carboxyl group, acrylate group, methacrylate group, carbinol The hydroxyl group or the hydroxyl group may be present at the end (one end or both ends) of the main chain, or may be present in the side chain. The leveling agent may have a polyether group at the end of the main chain or on a side chain. , polyurethane group, epoxy group, carboxyl group, acrylate group, methacrylate group, There are no particular limitations on the compounds as long as they have a carbinol group or a hydroxyl group. For example, silicone Silicone-based, fluorine-based, silicone / fluorine mixed, acrylic, methacrylic, aromatic Examples include belling agents.

[0077] Commercially available silicone leveling agents include, for example, BYK-300 and BYK -302, BYK-306, BYK-307, BYK-320, BYK-325, BYK -330, BYK-331, BYK-333, BYK-337, BYK-341, BYK -344, BYK-345, BYK-346, BYK-348, BYK-377, BYK -378, BYK-UV3500, BYK-3510, BYK-UV3570, etc. (without Examples include polyester-modified silicone oil (manufactured by BYK Japan Co., Ltd.). It can be obtained.

[0078] <Silane coupling agent> Silane coupling agents are organosilicon compounds that have reactive functional groups and hydrolyzable groups. The reactive functional group is a group that can react with a polyfunctional ionizing radiation polymerizable compound, etc. The functional groups include vinyl groups, epoxy groups, styryl groups, (meth)acryloyl groups, and amino groups. a thiol group, a ureido group, a sulfide group, and an isocyanate group; The functional groups may be one or more selected from the group consisting of:

[0079] The hydrolyzable group generates a silanol group (Si-OH) and an alcohol upon hydrolysis. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyl group. Oxy group, alkenyloxy group, carbamoyl group, amino group, aminooxy group, ketoxy When the hydrolyzable group has carbon atoms, the number of carbon atoms is 6 or more. It is preferable that the number of carbon atoms is 4 or less, and more preferable that the number of carbon atoms is 4 or less. A koxy group or an alkenyloxy group is preferred, and a methoxy group or an ethoxy group is preferred. Particularly preferred.

[0080] Specific examples of silane coupling agents include 3-methacryloyloxypropyl Methyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3- Methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyl Examples include propyltriethoxysilane and 3-acryloyloxypropyltriethoxysilane. Commercially available silane coupling agents include, for example, KBM-5103, K BM-502, KBM-503, KBE-502, KBE-503, KR-513 (Izu (This is also manufactured by Shin-Etsu Chemical Co., Ltd.)

[0081] <<Function layer>> The functional layer 16 is a layer that exhibits some function in the functional film 10. The layer 16 may be either an organic layer or an inorganic layer. When the functional layer 16 is an organic layer, In the present invention, the functional layer 16 can be formed by a coating method, and the functional layer 16 is an inorganic layer. In this case, it can be formed by a deposition method such as a sputtering method or a CVD method.

[0082] The functional layer 16 is not particularly limited, but may be, for example, an adhesion improving layer, an anti-reflection layer, a burr Examples of the layer include a conductive layer, an antiglare layer, an antistatic layer, an antifouling layer, and a combination thereof. The functional layer 16 shown in FIG. 1 is an anti-reflection layer. Specifically, as shown in FIG. 1, the functional layer 16 includes: The adhesion improving layer 17 may be composed of an adhesion improving layer 17 and an anti-reflection layer 18. may not be provided.

[0083] The thickness of the functional layer 16 is preferably 10 nm or more and 2 μm or less. If the film thickness of 6 is 10 nm or more, the desired function can be exhibited, and if it is 2 μm or less, If it is lower, damage due to residual stress during film formation of the functional layer 16 or expansion due to temperature or humidity changes may occur. The lower limit of the thickness of the functional layer 16 is 20 nm or more. It is more preferable that the upper limit of the thickness of the functional layer is 1 μm or less. In the case of a multi-layer structure, the thickness of the functional layer is the total thickness of each layer.

[0084] <Adhesion improving layer> The thickness of the adhesion improving layer 17 is preferably 15 nm or less. If the film thickness of 17 is 15 nm or less, the effect of improving adhesion can be obtained without affecting optical properties. The thickness of the adhesion-improving layer can be measured by scanning transmission electron microscope (STEM) or transmission electron microscope (TEM). Cross-sectional photographs of the adhesion-improving layer taken at 10,000 to 500,000 magnifications using a transmission electron microscope (TEM) The thickness is measured at 10 random locations, and the arithmetic mean value of the thicknesses measured at the 10 locations is used.

[0085] The adhesion improving layer 17 is an inorganic layer. Specifically, the adhesion improving layer 17 is made of SiN x Metal nitrides such as SiO x (x=1-2) and CrO x (x=1~2) and other metals It is composed of oxides.

[0086] The adhesion improving layer 17 can be formed by, for example, sputtering or ion plating. Physical vapor deposition (PVD) methods such as the annealing method and chemical vapor deposition (CVD) methods can be used. When the adhesion improving layer 17 is made of an inorganic material, the method for forming the adhesion improving layer is As the method, a sputtering method or a CVD method is preferable.

[0087] <Anti-reflection layer> The anti-reflection layer 18 is a layer that has the function of suppressing reflection of external light. When the anti-reflection layer has a multi-layer structure, the anti-reflection layer is made of a low refractive index layer. Alternatively, the optical film may have a laminated structure of a high refractive index layer, a low refractive index layer and a high refractive index layer.

[0088] The high refractive index layer is a layer having a refractive index higher than that of the low refractive index layer, and the refractive index of each layer is Ten pieces were taken out from each layer by cutting, etc., and the ten pieces were taken out. The refractive index of each layer was measured by the Becke method, and the average of 10 refractive indices of each layer was calculated. The Becke method uses a refractive index standard solution with a known refractive index, Place the fragment on a slide glass, etc., and drop a drop of refractive index standard solution onto the sample. The fragment was immersed in the standard liquid, and the state was observed under a microscope. The surface of the reinforced part and the refractive index standard were Bright lines (Becke lines) that appear on the surface of each layer due to the different refractive indices of the liquids can be visually observed. This method uses the refractive index of the refractive index standard solution that has run out as the refractive index of each layer.

[0089] The refractive index of the low refractive index layer is preferably 1.55 or less. The limit is more preferably 1.50 or less, and even more preferably 1.48 or less. The refractive index of the high refractive index layer may be 1.560 or more and 2.50 or less.

[0090] The thickness of the low refractive index layer is preferably 20 nm or more and 500 nm or less. The thickness of the low refractive index layer and the high refractive index layer is preferably 20 nm or more and 500 nm or less. The thickness of this layer can be measured by the same method as that for the adhesion improving layer 17.

[0091] <Barrier layer> The barrier layer is a layer that has the function of suppressing the permeation of moisture and oxygen. The material is not particularly limited as long as it has a barrier property. For example, silicon oxide, Examples of the inorganic material include inorganic oxides such as aluminum oxide and inorganic materials such as metals.

[0092] The thickness of the barrier layer is not particularly limited, but is preferably 0.01 μm or more and 1 μm or less. If the thickness of the barrier layer is 0.01 μm or more, the barrier performance of the barrier layer is sufficiently obtained. If the thickness is 1 μm or less, deterioration of the barrier performance due to cracks in the barrier layer can be suppressed. The more preferable lower limit of the thickness of the barrier layer is 0.03 μm or more, and the more preferable upper limit is 0.03 μm or more. is less than 0.5 μm.

[0093] The thickness of the barrier layer can be measured in the same manner as the thickness of the adhesion improving layer 17. The barrier layer may be a single layer or a laminate of multiple layers. When the barrier layer is a laminate of multiple layers, the thickness of the barrier layer is The film thickness refers to the total thickness of each layer.

[0094] The barrier layer can be formed by, for example, sputtering, ion plating, etc. Physical vapor deposition (PVD) and chemical vapor deposition (CVD) methods can be used. When the layer is made of an inorganic material, the CVD method is used as the barrier layer formation method. It is suitable.

[0095] <Conductive layer> The conductive layer is a layer having electrical conductivity. The conductive layer is made of, for example, an inorganic light-transmitting conductive material. , an organic light-transmitting conductive material, or an inorganic light-transmitting conductive material and an organic light-transmitting conductive material It includes materials mixed with conductive materials. Inorganic light-transmitting conductive materials include tin-doped oxide. Indium (ITO), antimony-doped tin oxide (ATO), zinc oxide, indium oxide In2O3, aluminum doped zinc oxide (AZO), gallium doped zinc oxide ( GZO), tin oxide, zinc oxide-tin oxide system, indium oxide-tin oxide system, zinc oxide- Examples include metal oxides such as indium oxide-magnesium oxide and carbon nanotubes. Among these, inorganic light transmitting materials are preferred from the viewpoint of transparency and low resistance in the transparent conductive layer. As the transparent conductive material, tin-doped indium oxide (ITO) is preferred. Examples of the bright conductive material include conductive polymers.

[0096] The thickness of the conductive layer is preferably 15 nm or more and 50 nm or less. It can be measured by the same method as that for the film thickness of the adhesion improving layer 17.

[0097] The method for forming the conductive layer is not particularly limited, and may be a sputtering method, a vacuum deposition method, an ion plating method, or the like. PVD methods such as coating, CVD methods, coating methods, printing methods, etc. can be used. When the layer is made of an inorganic light-transmitting conductive material, the conductive layer is formed by In this case, the PVD method is preferable.

[0098] <<Other functional films and hard-coated films>> The functional film 10 and the hard coat film 15 shown in FIG. 1 are made of a light-transmitting substrate 11. However, functional films and hard-coated films do not have a light-transmitting substrate. For example, the functional film 20 shown in FIG. The hard coat layer 12 includes the inorganic particles 14, and the hard coat layer 12 is adhered to the surface 12A of the hard coat layer 12. In the case of FIG. 3, the hard coat layer 16 is provided, but the light-transmitting substrate is not provided. The hard coat film is composed only of the hard coat layer 12. The members having the same reference numerals as those shown in FIG. 1 are the same as those shown in FIG. 1, and therefore the description thereof will be omitted. This shall be done.

[0099] <<Methods for manufacturing functional films and hard coat films>> The functional film 10 and the hard coat film 15 can be produced as follows. First, a coating agent is applied to one surface of the light-transmitting substrate 11 using a coating device such as a bar coater. The composition for hard coat layer is applied to form a coating film of the composition for hard coat layer.

[0100] <Hard Coat Layer Composition> The composition for the hard coat layer contains a polymerizable compound for forming the hard coat layer 12 and The composition for hard coat layer contains inorganic particles 14. In addition, the composition for hard coat layer may be, if necessary, Contains absorbents, leveling agents, silane coupling agents, solvents, polymerization initiators, and organic particles. That's fine.

[0101] (solvent) The solvent may be an alcohol (e.g., methanol, ethanol, propanol, isopropyl alcohol, etc.). Dopanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol, diacetone alcohol), ketones (e.g., acetone, methyl ethyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, heptane Tanone, diisobutyl ketone, diethyl ketone, diacetone alcohol), esters (acetic acid Methyl acetate, ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, methyl formate , PGMEA), aliphatic hydrocarbons (e.g., hexane, cyclohexane), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (e.g., benzene, benzene, toluene, xylene), amides (e.g., dimethylformamide, dimethylacetamide ethers (e.g., diethyl ether, dioxane, tetrahydrofuran, ether alcohols (e.g., 1-methoxy-2-propanol), carbonic acid These solvents include dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. The solvents may be used alone or in combination of two or more. In this case, components such as urethane (meth)acrylate and other additives are dissolved or dispersed. In addition, methyl isobutyl ketone is preferred in that the composition for the first hard coat layer can be suitably applied. Methyl ethyl ketone is preferred.

[0102] (Polymerization initiator) The polymerization initiator is decomposed by irradiation with ionizing radiation to generate radicals, which then initiate the polymerization of the polymerizable compound. It is a component that initiates or advances cross-linking.

[0103] Polymerization initiators release substances that initiate radical polymerization when exposed to ionizing radiation. There is no particular limitation as long as it is possible. The polymerization initiator is not particularly limited, and known ones can be used. Specific examples include acetophenones, benzophenones, Michler's compounds, and the like. Benzoyl benzoates, α-amyloxime esters, thioxanthones, propiophen Examples of the acylphosphine oxides include non-acylphosphine oxides, benzyl phosphine oxides, benzoin phosphine oxides, and acylphosphine oxides. It is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butyl acetate. amine, triethylamine, poly-n-butylphosphine, etc.

[0104] After forming a coating film of the composition for hard coat layer, the coating film is dried by various known methods for, for example, 30 minutes. Dry the film by heating it at a temperature between 10°C and 120°C for 10 to 120 seconds, and remove the solvent. Allow to evaporate.

[0105] After the coating is dried, it is irradiated with ionizing radiation such as ultraviolet light to harden the coating (complete hardening). ) to form the hard coat layer 12.

[0106] After forming the hard coat layer 12, the surface of the hard coat layer 12 is etched to remove the hard coat layer. To obtain a coated film 15, specifically, the binder resin near the surface of the hard coat layer 12 is The binder resin 13 is selectively etched, which may expose the inorganic particles 14. The method for selectively etching the resin 13 includes, for example, glow discharge treatment and plasma treatment. However, the presence of an adhesion improving layer can If sufficient adhesion can be obtained, the etching step may be omitted.

[0107] After etching the surface 12A of the hard coat layer 12, for example, a method such as sputtering is used. The adhesion improving layer 17 and the anti-reflection layer 18 are formed by vapor deposition to form the functional layer 16. In this way, the functional film 10 is obtained.

[0108] The optical functional film 20 and the hard coat film shown in FIG. 3 are formed by applying a hard coat to a release film. The hard coat layer 12 and the functional layer 16 are formed in the same manner as above. After the functional layer 16 is formed, The release film is peeled off to obtain the desired shape.

[0109] According to this embodiment, the density of the inorganic particles 14 in the first region R1 is high, that is, 60% or more. Since the dense layer region exists, the hard coat layer 12 has no inclusions near the surface 12A. Therefore, on the surface 12A of the hard coat layer 12, In general, inorganic substances with similar compositions tend to adhere to each other. Therefore, when the functional layer 16 is an inorganic layer, the hard coat layer 12 is made of a binder resin. Even though the layer contains the functional layer 16, it can have good adhesion to the functional layer 16. Even when the functional layer 16 is an organic layer, the hard coat layer 12 is made of a binder resin 1 Since the layer contains 3, it is possible to make the adhesion to the functional layer 16 good. This can improve the adhesion between the hard coat layer 12 and the functional layer 16. Since the density of the inorganic particles 14 in the second region R2 is 59% or less, This can prevent the deterioration of optical properties caused by too many molecules 14. It is possible to achieve both adhesion between the adhesive layer 12 and the functional layer 16 and desired optical properties. .

[0110] <<<Polarizing plate>>> The functional film 10 and the hard coat film 15 are used, for example, by being incorporated into a polarizing plate. In this embodiment, the functional film 10 and the hard coat film The film 15 is used as a protective film for the polarizer, but the functional film 10 and the The use of the hard coat film 15 is not particularly limited.

[0111] As shown in FIG. 4, the polarizing plate 30 is a polarizing plate for the functional film 10 and the light of the functional film 10. The second surface 11A of the transparent substrate 11 is opposite to the first surface 11A on the hard coat layer 12 side. 1B side and the polarizer 31 on the side opposite to the functional film 10 side of the polarizer 31 The protective film 32 is a retardation film. It is also possible.

[0112] The polarizer 31 is made of a uniaxially stretched polyvinyl alcohol dyed with iodine or a dichroic dye. Examples of polyvinyl alcohol resins include polyvinyl acetate. The polyvinyl acetate resin may be a saponified vinyl resin. In addition to polyvinyl acetate, which is a vinyl homopolymer, there are also vinyl acetate and other copolymerizable monomers. Other monomers that can be copolymerized with vinyl acetate include, for example, For example, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, ammonium Examples of the acrylamide include acrylamides having an ammonium group.

[0113] The polyvinyl alcohol resin may be modified, for example, by aldehydes. Polyvinyl formal, polyvinyl acetal, etc. can also be used.

[0114] Such functional film 10, hard coat film 15 and polarizing plate 30 may be, for example, It can be incorporated into an image display device for use.

[0115] <<<Image display devices>>> As shown in FIG. 5, the image display device 40 mainly includes a display panel for displaying images. 40 and a backlight device 60 disposed on the rear side of the display panel 50. In this embodiment, the display panel 50 is a liquid crystal display panel, so the image display device 40 is Although a backlight device 60 is provided, depending on the type of display panel (display element), The light device 60 does not have to be provided.

[0116] <<Display panel>> As shown in FIG. 5, the display panel 50 is oriented from the backlight device 60 side toward the viewer side. The polarizing plate 51, the light-transmitting adhesive layer 52, the display element 53, the light-transmitting adhesive layer 54, the ...4, the polarizing plate 51, the light-transmitting adhesive layer 52, the display element 53, the light The display panel 50 has a structure in which the polarizing plate 30 is laminated in this order. The polarizing plate 51 and the like may not be provided.

[0117] The polarizing plate 51 includes a protective film 55, a polarizer 56, and a protective film 57 in this order. The protective films 55 and 57 are made of triacetyl cellulose film (TAC film). The polarizer 56 is made of a polarizing film. Since it is similar to the child 21, the explanation will be omitted here.

[0118] The display element 53 is a liquid crystal display element. However, the display element 53 is not limited to a liquid crystal display element. , e.g., organic light emitting diodes (OLEDs), inorganic light emitting diodes, and / or quantum The display element may be a QLED (Quantum Dot Light Emitting Diode) display element. The LCD is a public display that has a liquid crystal layer, an alignment film, an electrode layer, a color filter, etc., placed between two glass substrates. It is possible to use a known liquid crystal display element.

[0119] <<Backlight device>> The backlight device 60 illuminates the display panel 50 from the rear side of the display panel 50. As the backlight device 60, a known backlight device can be used. The backlight device 60 may be either an edge light type or a direct type. That's fine. [Example]

[0120] In order to explain the present invention in detail, the following examples are given. Not limited to the description.

[0121] The components were mixed so as to obtain the composition shown below, thereby obtaining a composition for a hard coat layer. (Hard Coat Layer Composition 1) Pentaerythritol triacrylate and pentaerythritol tetraacrylate Mixture (monomer, product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 27.4 parts by mass Isocyanuric acid EO modified di- and triacrylate (monomer, product name "M-313") , manufactured by Toagosei Co., Ltd.): 25.0 parts by mass Polymethyl methacrylate (PMMA) polymer 25% solution (toluene:anone = 9:1) Solution, product name "HRAG Acrylic", manufactured by DNP Fine Chemicals Co., Ltd.): 12.0 weight Amount Silica particles (particle size 25 nm measured by BET method, product name "ELECOM V8803- 25", manufactured by JGC Catalysts and Chemicals Co., Ltd.): 37.5 parts by mass Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacur e (registered trademark) 184" manufactured by BASF Japan Ltd.): 6.5 parts by mass Polymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane) 1-One, product name "Irgacure® 907", BASF Japan Ltd. ): 1.5 parts by mass Toluene (solvent, product name "Toluol", manufactured by DIC Graphics Co., Ltd.): 108. 2 parts by mass Cyclohexanone (solvent, product name "Anon", manufactured by Yamaichi Chemical Industry Co., Ltd.): 24.5g Amount Normal butanol: 37.0 parts by mass Methyl isobutyl ketone (solvent, product name "4-methyl-n-2-pentanone", Kanto Chemical) Co., Ltd.): 36.9 parts by mass

[0122] (Hard Coat Layer Composition 2) Pentaerythritol triacrylate and pentaerythritol tetraacrylate Mixture (monomer, product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 37.5 parts by mass Isocyanuric acid EO modified di- and triacrylate (monomer, product name "M-313") , manufactured by Toagosei Co., Ltd.): 25.0 parts by mass Polymethyl methacrylate (PMMA) polymer 25% solution (toluene:anone = 9:1) Solution, product name "HRAG Acrylic", manufactured by DNP Fine Chemicals Co., Ltd.): 12.0 weight Amount Silica particles (particle size 25 nm measured by BET method, product name "ELECOM V8803- 25", manufactured by JGC Catalysts and Chemicals Co., Ltd.): 37.5 parts by mass ·Organic particles (product name "504TNR", manufactured by Sekisui Plastics Co., Ltd.): 2.2 parts by mass Organic particles (particle size 3.5 μm, product name "Soliostar RA-E35FX", Japan Co., Ltd. Catalyst): 9.5 parts by mass Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacur e (registered trademark) 184" manufactured by BASF Japan Ltd.): 6.5 parts by mass Polymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropanol) Irgacure® 907 (product name: Irgacure® 907), BASF Japan Co., Ltd. Company: 1.5 parts by mass Toluene (solvent, product name "Toluol", manufactured by DIC Graphics Co., Ltd.): 108. 2 parts by mass Cyclohexanone (solvent, product name "Anon", manufactured by Yamaichi Chemical Industry Co., Ltd.): 24.5g Amount Normal butanol: 37.0 parts by mass Methyl isobutyl ketone (solvent, product name "4-methyl-n-2-pentanone", Kanto Chemical) Co., Ltd.): 36.9 parts by mass

[0123] (Hard Coat Layer Composition 3) Pentaerythritol triacrylate and pentaerythritol tetraacrylate Mixture (monomer, product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 48 parts by mass Isocyanuric acid EO modified di- and triacrylate (monomer, product name "M-313") , manufactured by Toagosei Co., Ltd.): 32.0 parts by mass Polymethyl methacrylate (PMMA) polymer 25% solution (toluene:anone = 9:1) Solution, product name "HRAG Acrylic", manufactured by DNP Fine Chemicals Co., Ltd.): 12.0 weight Amount Silica particles (particle size 25 nm measured by BET method, product name "ELECOM V8803- 25", manufactured by JGC Catalysts and Chemicals Co., Ltd.): 30.0 parts by mass ·Organic particles (product name "504TNR", manufactured by Sekisui Plastics Co., Ltd.): 2.2 parts by mass Organic particles (particle size 3.5 μm, product name "Soliostar RA-E35FX", Japan Co., Ltd. Catalyst): 9.5 parts by mass Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacur e (registered trademark) 184" manufactured by BASF Japan Ltd.): 6.5 parts by mass Polymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropanol) Irgacure® 907 (product name: Irgacure® 907), BASF Japan Co., Ltd. Company: 1.5 parts by mass Toluene (solvent, product name "Toluol", manufactured by DIC Graphics Co., Ltd.): 108. 2 parts by mass Cyclohexanone (solvent, product name "Anon", manufactured by Yamaichi Chemical Industry Co., Ltd.): 24.5g Amount Normal butanol: 37.0 parts by mass Methyl isobutyl ketone (solvent, product name "4-methyl-n-2-pentanone", Kanto Chemical) Co., Ltd.): 36.9 parts by mass

[0124] (Hard Coat Layer Composition 4) Pentaerythritol triacrylate and pentaerythritol tetraacrylate Mixture (monomer, product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 35.0 parts by mass Isocyanuric acid EO modified di- and triacrylate (monomer, product name "M-313") , manufactured by Toagosei Co., Ltd.): 25.0 parts by mass Polymethyl methacrylate (PMMA) polymer 25% solution (toluene:anone = 9:1) Solution, product name "HRAG Acrylic", manufactured by DNP Fine Chemicals Co., Ltd.): 12.0 weight Amount Silica particles (particle size 25 nm measured by BET method, product name "ELECOM V8803- 25", manufactured by JGC Catalysts and Chemicals Co., Ltd.): 40.0 parts by mass ·Organic particles (product name "504TNR", manufactured by Sekisui Plastics Co., Ltd.): 2.2 parts by mass Organic particles (particle size 3.5 μm, product name "Soliostar RA-E35FX", Japan Co., Ltd. Catalyst): 9.5 parts by mass Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacur e (registered trademark) 184" manufactured by BASF Japan Ltd.): 6.5 parts by mass Polymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropanol) Irgacure® 907 (product name: Irgacure® 907), BASF Japan Co., Ltd. Company: 1.5 parts by mass Toluene (solvent, product name "Toluol", manufactured by DIC Graphics Co., Ltd.): 108. 2 parts by mass Cyclohexanone (solvent, product name "Anon", manufactured by Yamaichi Chemical Industry Co., Ltd.): 24.5g Amount Normal butanol: 37.0 parts by mass Methyl isobutyl ketone (solvent, product name "4-methyl-n-2-pentanone", Kanto Chemical) Co., Ltd.): 36.9 parts by mass

[0125] (Hard Coat Layer Composition 5) Pentaerythritol triacrylate and pentaerythritol tetraacrylate Mixture (monomer, product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 37.5 parts by mass Isocyanuric acid EO modified di- and triacrylate (monomer, product name "M-313") , manufactured by Toagosei Co., Ltd.): 25.0 parts by mass Polymethyl methacrylate (PMMA) polymer 25% solution (toluene:anone = 9:1) Solution, product name "HRAG Acrylic", manufactured by DNP Fine Chemicals Co., Ltd.): 12.0 weight Amount Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacur e (registered trademark) 184" manufactured by BASF Japan Ltd.): 6.5 parts by mass Polymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropanol) Irgacure® 907 (product name: Irgacure® 907), BASF Japan Co., Ltd. Company: 1.5 parts by mass Toluene (solvent, product name "Toluol", manufactured by DIC Graphics Co., Ltd.): 108. 2 parts by mass Cyclohexanone (solvent, product name "Anon", manufactured by Yamaichi Chemical Industry Co., Ltd.): 24.5g Amount Normal butanol: 37.0 parts by mass Methyl isobutyl ketone (solvent, product name "4-methyl-n-2-pentanone", Kanto Chemical) Co., Ltd.): 36.9 parts by mass

[0126] (Hard Coat Layer Composition 6) Pentaerythritol triacrylate and pentaerythritol tetraacrylate Mixture (monomer, product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 6.9 parts by mass Reactive polymer (product name "Hitaroid 7988", manufactured by Hitachi Chemical Co., Ltd.): 26.6% Amount Silica particle dispersion (particle size measured by BET method: 40 nm to 50 nm, solid content: 30 mass %, Dispersion medium isopropanol (MIBK), product name "MIBK-ST-L", Nissan Chemical Industries, Ltd. (Manufactured by the Company): 25.3 parts by mass Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacur e (registered trademark) 184" manufactured by BASF Japan Ltd.): 4.6 parts by mass Methyl isobutyl ketone (solvent, product name "4-methyl-n-2-pentanone", Kanto Chemical) Co., Ltd.): 36.9 parts by mass γ-Butyllactone (product name: γ-Butyllactone, manufactured by Mitsubishi Scientific Corporation): 3.8 Mass part

[0127] (Hard Coat Layer Composition 7) Multifunctional urethane acrylate (product name "KAYARAD DPHA-40H", Nippon Kagaku Pharmaceutical Co., Ltd.): 186 parts by mass Pentaerythritol triacrylate (product name "A-TMM-3L", Shin-Nakamura Chemical Co., Ltd.) Co., Ltd.): 167 parts by mass Polymer acrylate (product name "BS371", manufactured by Arakawa Chemical Industries, Ltd.): 246 Amount 2-Methacryloyloxyethyl Acid Phosphate (product name: Light Ester P-1M ", manufactured by Kyoeisha Chemical Co., Ltd.): 27 parts by mass Silica particle dispersion (particle size measured by BET method: 40-50 nm, solid content: 30 mass%, dispersion Methyl isobutyl ketone (MIBK), product name "MIBK-SD-L", Nissan Chemical Industries Co., Ltd.): 889 parts by mass Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacur e (registered trademark) 184" manufactured by BASF Japan Ltd.): 36 parts by mass Silicone leveling agent (product name "BYK-377", BYK Japan Co., Ltd.) ): 0.6 parts by mass Triazine-based UV absorber (product name: Tinuvin 477, BASF Japan Co., Ltd.) Company: 11 parts by weight Silane coupling agent (product name "KR-513", manufactured by Shin-Etsu Chemical Co., Ltd.): 43 Amount Propylene glycol monomethyl ether acetate (solvent, DNP Fine Co., Ltd.) Chemical): 370 parts by mass Butyl acetate (solvent, manufactured by DNP Fine Chemicals Co., Ltd.): 75 parts by weight Cyclohexanone (solvent, manufactured by DNP Fine Chemicals Co., Ltd.): 352 parts by mass

[0128] The components were mixed so as to obtain the composition shown below to obtain a composition for an undercoat layer. (Base layer composition 1) Multifunctional urethane acrylate (product name "KAYARAD DPHA-40H", Nippon Kagaku Pharmaceutical Co., Ltd.): 98 parts by mass Pentaerythritol triacrylate (product name "A-TMM-3L", Shin-Nakamura Chemical Co., Ltd.) Co., Ltd.): 88 parts by mass Polymer acrylate (product name "BS371", manufactured by Arakawa Chemical Industries, Ltd.): 129g Amount 2-Hydroxyethyl methacrylate (product name: 2-Hydroxyethyl methacrylate) ", manufactured by Tokyo Chemical Industry Co., Ltd.): 270 parts by mass Amount Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacur e (registered trademark) 184" manufactured by BASF Japan Ltd.): 36 parts by mass Silicone leveling agent (product name "BYK-377", BYK Japan Co., Ltd.) ): 0.6 parts by mass Triazine-based UV absorber (product name: Tinuvin 477, BASF Japan Co., Ltd.) Company: 11 parts by weight Silane coupling agent (product name "KR-513", manufactured by Shin-Etsu Chemical Co., Ltd.): 43 Amount Propylene glycol monomethyl ether acetate (solvent, DNP Fine Co., Ltd.) Chemical): 300 parts by mass Butyl acetate (solvent, manufactured by DNP Fine Chemicals Co., Ltd.): 102 parts by weight Cyclohexanone (solvent, manufactured by DNP Fine Chemicals Co., Ltd.): 285 parts by mass γ-butyrolactone (solvent, manufactured by Mitsubishi Chemical Corporation): 151 parts by mass

[0129] Example 1 First, a triacetyl cellulose film (product name: 80 μm thick) was used as a light-transmitting substrate. A triacetyl cellulose film (TD80UL, manufactured by Fujifilm Corporation) was prepared. The hard coat layer composition 1 was applied to one surface of the film to form a coating film. The coating was dried by passing dry air at 70°C for 60 seconds. The solvent is evaporated and the integrated amount of ultraviolet light is 100 mJ / cm 2 The coating is irradiated so that By curing, a hard coat layer having a thickness of 5 μm was formed.

[0130] After forming the hard coating layer, the surface of the hard coating layer was treated with a treatment intensity of 80 W·min / m 2 A glow discharge treatment was carried out at 1000 kJ / min ..., thereby obtaining a hard coat film.

[0131] A cross-sectional photograph of the hard coat layer taken with a scanning transmission electron microscope (STEM) shows that the hard The shape of the silica particles in the coating layer was confirmed to be spherical. The average primary particle size of the silica particles was measured and found to be 25 nm. The particle size was measured using scanning transmission electron microscope (STEM) images taken at magnifications of 40,000 to 200,000. The particle sizes of 20 silica particles were measured from the cross-sectional image of the silica particles, and the particle sizes of the 20 silica particles were The thickness of the hard coat layer was measured by scanning transmission electron microscope (STE) M) to photograph a cross section of the hard coat layer, and the hard coat layer is The film thickness was measured at 20 points, and the arithmetic mean value of the film thicknesses at the 20 points was used.

[0132] A cross-sectional photograph of the hard coat layer taken with a scanning transmission electron microscope (STEM) is shown below. First, a hard-coated film was cut into a size of 15mm x 10mm. The specimen was fixed on a resin plate and then microtomed using a microtome EM UC6 (Leica Microsystems). After cutting to a width of 300 μm and a height of 80 μm using a trimming machine (manufactured by DiATOME), The diamond knife ULTRA cuts in the thickness direction, leaving a uniform, hole-free finish. A section with a thickness of 80 nm was cut out. This uniform section without holes was used as the measurement sample. After that, a scanning transmission electron microscope (STEM) (product name "S-4800", manufactured by A cross-sectional photograph of the measurement sample was taken using a microscope (Hitachi High-Technologies Corporation). When taking cross-sectional photographs using the 800, the detector should be set to "TE" and the accelerating voltage to "30kV." The cross-section was observed with the emission current set to 10 μA. Adjust the contrast and brightness to 40,000x to 10,000x while observing whether each layer can be distinguished. The magnification was adjusted appropriately. When taking cross-sectional photographs using the S-4800, Then, set the beam monitor aperture to "3", the objective lens aperture to "3", and the WD to " In the other examples and comparative examples, the same method as in Example 1 was used to make the silicon dioxide particles. The particle shape was confirmed, and the average primary particle size and the film thickness of the hard coat layer and functional layer were measured. .

[0133] <Example 2> In Example 2, composition 2 for hard coat layer was used instead of composition 1 for hard coat layer. A hard coat film was obtained in the same manner as in Example 1, except that the above was used.

[0134] Example 3 In Example 3, composition 3 for hard coat layer was used instead of composition 1 for hard coat layer. A hard coat film was obtained in the same manner as in Example 1, except that the above was used.

[0135] Example 4 In Example 4, composition 4 for hard coat layer was used instead of composition 1 for hard coat layer. A hard coat film was obtained in the same manner as in Example 1, except that the above was used.

[0136] <Example 5> In Example 5, hardening was carried out in the same manner as in Example 1, except that the drying temperature was set to 50°C. A coated film was obtained.

[0137] Example 6 First, the surface of the hard coat film obtained in Example 1 (the surface of the hard coat layer) was SiO film with a thickness of 5 nm was deposited by sputtering. x (x=1 to less than 2) Furthermore, an anti-reflection layer was formed on the surface of the adhesion improving layer by a sputtering method, This forms a functional layer consisting of an adhesion improving layer and an anti-reflection layer, and a functional film is obtained. The anti-reflection layer is made up of, from the bottom up, a high refractive index layer made of Nb2O5 with a thickness of 20 nm, a SiO a 35 nm thick low refractive index layer made of Nb2O5; The multilayer structure consisted of a low refractive index layer made of SiO2 and a 100 nm thick layer made of SiO2. The refractive indexes of the high refractive index layer and the low refractive index layer were measured by the Becke method. The refractive index of the low refractive index layer was 2.3 and that of the low refractive index layer was 1.48.

[0138] Example 7 In Example 7, the surface of the hard coat film obtained in Example 2 was coated with the same film as in Example 6. A functional layer consisting of an adhesion improving layer and an anti-reflection layer is formed by the same method, and a functional film is formed. I got the film.

[0139] Example 8 In Example 8, the surface of the hard coat film obtained in Example 3 was coated with the same film as in Example 6. A functional layer consisting of an adhesion improving layer and an anti-reflection layer is formed by the same method, and a functional film is formed. I got the film.

[0140] Example 9 In Example 9, the surface of the hard coat film obtained in Example 4 was coated with the same film as in Example 6. A functional layer consisting of an adhesion improving layer and an anti-reflection layer is formed by the same method, and a functional film is formed. I got the film.

[0141] Example 10 In Example 10, the surface of the hard coat film obtained in Example 5 was coated with the film of Example 6. A functional layer consisting of an adhesion improving layer and an anti-reflection layer is formed by the same method as in The film was obtained.

[0142] <Comparative Example 1> In Comparative Example 1, composition 5 for hard coat layer was used instead of composition 1 for hard coat layer. A hard coat film was obtained in the same manner as in Example 1, except that the above was used.

[0143] <Comparative Example 2> In Comparative Example 2, composition 6 for hard coat layer was used instead of composition 1 for hard coat layer. Instead of triacetyl cellulose film, a 40 μm thick acrylic resin film was used. A hard coat film was obtained in the same manner as in Example 1, except that a film was used.

[0144] <Comparative Example 3> First, a 40 μm thick acrylic resin film was prepared as a substrate. The undercoat layer composition 1 was applied to one surface of the film to form a coating film. The coating is dried by passing dry air at 70°C through it for 60 seconds. is evaporated, and the accumulated amount of ultraviolet light is 100mJ / cm 2 The coating is hardened by irradiating it so that By this, an underlayer having a thickness of 4 μm was formed.

[0145] After forming the underlayer, the hard coat layer composition 7 is applied to the surface of the underlayer to form a coating film. Next, dry air at 70°C was passed through the formed coating for 60 seconds to dry it. This evaporates the solvent in the coating, and the integrated amount of ultraviolet light reaches 100 mJ / cm 2 It will be The coating was cured by irradiation in this manner to form a hard coat layer with a thickness of 5 μm.

[0146] <Comparative Example 4> In Comparative Example 4, the surface of the hard coat film obtained in Comparative Example 1 was coated with the same film as in Example 6. A functional layer consisting of an adhesion improving layer and an anti-reflection layer is formed by the same method, and a functional film is formed. I got the film.

[0147] <Comparative Example 5> In Comparative Example 5, the surface of the hard coat film obtained in Comparative Example 2 was coated with the same film as in Example 6. A functional layer consisting of an adhesion improving layer and an anti-reflection layer is formed by the same method, and a functional film is formed. I got the film.

[0148] <Comparative Example 6> In Comparative Example 6, the surface of the hard coat film obtained in Comparative Example 3 was coated with the same film as in Example 6. A functional layer consisting of an adhesion improving layer and an anti-reflection layer is formed by the same method, and a functional film is formed. I got the film.

[0149] <Density of silica particles> In the hard coat films and functional films according to the examples and comparative examples, a first region in the hard coating layer extending from the surface of the hard coating layer to a depth of 100 nm; In the second region at a depth of 100 nm or more from the surface of the hard coating, the density of the silica particles is The density was measured. Specifically, the density of the silica particles in the first region was measured by the following method. First, a scanning transmission electron microscope (STEM) (product name: S-4800, The hard coat images were taken at a magnification of 30,000 to 100,000 using a microscope (Hitachi High-Technologies Corporation). The cross-sectional image of the layer (see Fig. 6) was processed using image processing software (product name "ImageJ", USA) The data was read using a scanner (manufactured by the National Institutes of Health) and binarized into black and white for each cell. The number of pixels in the image was set to 640 × 480 or more. Silica particles with high density are difficult to transmit electron beams, so they appear black. The binder resin with low color density turned white. Therefore, the silica particles turned black after binarization. The binder resin appeared as a white part. The area on the white side of the average value of the particle size was considered to be the resin part, and the area on the black side was considered to be the particle part. Then, among the cells appearing in the image after binarization, the cells perpendicular to the film thickness direction of the hard coat layer were A row of cells arranged in the intersecting direction is considered to be one column, and each cell in the column is either black or white. The number of cells judged as black parts relative to the total number of cells in one column is calculated. In the first region, the entire region was analyzed, and the proportion (%) of silica particles was calculated. The maximum density of silica particles in the second region was also determined. The density of silica particles is calculated in the same way as that of silica particles in the second region, but in the second region, the density is calculated at different depths. The above ratios for five columns are calculated, and the arithmetic mean value is calculated to obtain the second region. The density of silica particles was determined as

[0150] The cross-sectional photograph of the hard coat layer was taken by STEM using the following method. Hard coat film or functional film cut into 15mm x 10mm size is The specimen was fixed on a plate and then microtomed using a microtome EM UC6 (Leica Microsystems). After cutting to a width of 300 μm and a height of 80 μm, The Diamond Knife ULTRA cuts in the thickness direction, leaving a uniform thickness without holes. Sections of 80 nm were cut out. Then, a STEM (product name "S-4800", Nihon University Corporation) was used. The cross-sectional photographs of the measurement samples were taken using a microscope (manufactured by Tateishi High Technologies). When taking cross-sectional photographs using 00, the detector is set to "TE", the acceleration voltage is set to "30kV", The cross-section was observed with the emission current set to 10 μA. Adjust the contrast and brightness to 40,000 to 150,000 times while observing whether each layer can be distinguished. When taking cross-sectional photographs using the S-4800, Set the beam monitor aperture to "3", the objective lens aperture to "3", and the WD to "8 I set it to "mm".

[0151] The above binarization process was performed using image processing software (product name: ImageJ, National Institutes of Health, USA). Specifically, the following procedure was performed: The cross-sectional photograph image is loaded and one pixel is counted as one cell in the spreadsheet software. The gradation of black was output as a numerical value (see Figure 7). The number of gradations was set to 255. Scanning transmission electron microscope photograph of a cross section of the hard coat layer in the functional film according to Example 1 7 is a graph showing the results of the calculation using spreadsheet software for the hard coat film according to Example 1. This is the image after being binarized.

[0152] <Maximum degree of silica particle aggregation in the second region> In the hard coat films and functional films according to the examples and comparative examples, The maximum degree of aggregation of silica particles in the region of The black and white binarization process was carried out using the same method and conditions as in the measurement of the density of the Among the cells appearing in the image after black and white binarization, the cells perpendicular to the film thickness direction of the hard coat layer A row is made up of multiple cells aligned in the same direction, and the length of the cells is at least three times the primary particle size of the silica particles. The number of cells that are continuous is judged to be in an aggregated state, and the silica The percentage of cells that are continuous with a length of at least three times the primary particle diameter of the particles is calculated. The degree of aggregation of the silica particles was calculated. The largest degree of aggregation among the silica particles was taken as the maximum degree of aggregation.

[0153] <Adhesion> In the hard coat films and functional films according to the examples and comparative examples, adhesion The hard coat film was evaluated for its properties by the cross-cut method. By the above method, an adhesion improving layer is applied to the surface of the hard coat film (surface of the hard coat layer). The adhesion was evaluated with the anti-reflection layer formed on the surface. Specifically, the adhesion was evaluated in accordance with JIS K5600-5-6:1999. Based on this, a cross-cut CCJ-1 (manufactured by Cortec) was used to measure the surface after the anti-reflection layer was formed. Then, a checkerboard pattern was made on the surface of the hard coat film and the functional film. 100 squares of 24 mm square were made. Apply Tape (registered trademark) to the grid, then rub it back and forth 10 times with a spatula to make sure it adheres. This operation was repeated five times, and the number of remaining squares was counted. The number of remaining squares was used as the numerator and the total number of squares as the denominator, and the results were evaluated according to the following criteria: . ◎:100 / 100 ○: 91 / 100 or more and 99 / 100 or less △:50 / 100 or more and 90 / 100 or less ×: Less than 50 / 100

[0154] <Haze value> The haze values ​​of the hard coat films according to Examples 1 to 5 and Comparative Examples 1 and 2 were measured. The haze value was measured using a haze meter (product name "HM-150", Murakami Color Technology Co., Ltd.). The measurement was carried out using a method conforming to JIS K7136:2000 using a meter manufactured by the Research Institute. The haze value was measured by cutting out a functional film into a piece of 50mm x 50mm and then checking for curls and wrinkles. The anti-reflection layer side is placed on the non-light source side in an environment free of fingerprints, dust, etc., and the function is confirmed. Measurement was carried out three times for each sheet of film, and the arithmetic mean value of the three measurements was used. The hard coat films according to Example 1 and Comparative Examples 1 to 3 do not exhibit antiglare properties. Since the film is designed as a film, the lower the haze value, the better. The hard coat film is designed to have anti-glare properties, The size value is 6% or more and 20% or less, and the 60° gloss value described below is 70% or more and 110% or less. It is preferable that:

[0155] <Total light transmittance> The total light transmittance of the hard coat films according to Examples 1 to 5 and Comparative Examples 1 and 2 is shown below. The total light transmittance was measured using a haze meter (product name "HM-150" manufactured by Murakami Co., Ltd.). (manufactured by Color Research Laboratory) and measured according to the method in accordance with JIS K7361-1:1997 The total light transmittance was measured by cutting the functional film into a piece measuring 50 mm x 50 mm. After that, the anti-reflection layer side is placed on the non-light source side without curling or wrinkles, fingerprints, dust, etc. The measurement was carried out three times for each functional film, and the arithmetic mean of the three measurements was calculated. The higher the total light transmittance, the more preferable it is.

[0156] <60° gloss value> The 60° gloss values ​​of the hard coat films according to Examples 1 to 5 and Comparative Example 1 were The 60° gloss values ​​were measured using a precision gloss meter (product name "GM-26D" manufactured by Murakami Co., Ltd.). Measured using a colorimeter manufactured by Color Research Institute in accordance with JIS Z8741:1997 The above 60° gloss values ​​were measured by cutting the functional film into a size of 50 mm x 50 mm. After that, the back side of the hard coat film was attached to a non-glossy black resin plate by air suction. The 60° gloss value was measured using a precision gloss meter. Each sheet was measured three times, and the arithmetic mean value of the three measurements was calculated.

[0157] <Element ratio in the hard coat layer> In the hard coat films according to Example 2 and Comparative Example 2, the hard coat layer was The element ratios of C, N, O, and Si were varied by etching in the direction of the surface and changing the depth from the surface. Specifically, a scanning X-ray photoelectron spectrometer (product name: Quantum2000 "), manufactured by ULVAC-PHI, Inc., was used under the following measurement conditions to measure the depth of 100 mm from the surface. The element ratios of C, N, O, and Si were determined every 5 nm in the region up to nm. (Measurement conditions) ·X-ray conditions: Al mono 200μmφ×30W 15kV, Photoelectron capture angle: 45° Etching conditions: 2kV raster 2×2

[0158] The results for the hard coat film are shown in Table 1, and the results for the functional film are shown in Table 2. The elements C, N, O, and Si in the hard coat layers according to Example 2 and Comparative Example 2 are shown in Table 1. The ratios are shown in Table 3. [Table 1]

[0159] [Table 2]

[0160] [Table 3]

[0161] As shown in Table 1, the hard coat films according to Comparative Examples 1 and 2 were poor in adhesion. This is because the density of silica particles in the first region of the hard coat layer is 60% or more. This is thought to be because there were no areas where silica particles were present and there were many silica particles in the second area. The hard coat film according to Comparative Example 3 had good adhesion, but In contrast, the hard coat film according to Example 1 had a high hard coat layer. The first region has a portion where the density of silica particles is 60% or more, and the second region has a portion where the density of silica particles is 60% or more. Because there are few silica particles in the area, it has excellent adhesion, high total light transmittance, and 6 shows the hard coat layer of the hard coat film according to Example 1. This is a scanning transmission electron microscope photograph of a cross section, and it can be seen from this photograph that the surface of the hard coat layer is It can be seen that there are more silica particles in the area than in other areas. The hard coat film also has a silica particle density of 60% or more in the first region of the hard coat layer. Since there is a top portion and there are few silica particles in the second region, adhesion The total light transmittance was high, and the haze value and 60° gloss value were also within the desired range. .

[0162] In addition, as shown in Table 2, the functional films according to Comparative Examples 4 and 5 were inferior in adhesion. This is because the density of silica particles in the first region of the hard coat layer is 60% or more. This is thought to be because there were no areas where silica particles were present and there were many silica particles in the second area. The functional film according to Comparative Example 6 had good adhesion, but the adhesiveness was not as good as that of Comparative Example 3. Since such a hard coat film is used, the same properties as the hard coat film according to Comparative Example 3 are obtained. In contrast, the haze value of the functional film according to Example 6 is considered to be high. The hard coat layer has a first region in which the density of silica particles is 60% or more. At the same time, the second region contained fewer silica particles, which resulted in excellent adhesion. The functional film according to Example 6 uses the hard coat film according to Example 1. Therefore, similar to the hard coat film of Example 1, the total light transmittance is high and It is considered that the hardness value is lowered. The first region of the hard coating layer has a portion where the density of silica particles is 60% or more. Since the number of silica particles present in the second region is small, the adhesion was excellent. The functional films according to Examples 7 to 10 use the hard coat films according to Examples 2 to 5. Therefore, similar to the hard coat films according to Examples 2 to 5, the total light transmittance is high and the haze is good. It is believed that the saturation value and 60° gloss value will also fall within the desired range.

[0163] Furthermore, as shown in Table 3, in the hard-coated film according to Example 2, In the region from the surface of the hard coating layer to a depth of 10 nm to 30 nm, the total element ratio of Si and O is In other regions, the total element ratio of Si and O was less than 60%. This shows that silica particles are concentrated in the region of 10 nm to 30 nm in depth, but in other regions Therefore, it is considered that the hard coat film according to Example 2 was uniformly distributed. In this system, the hard coat layer is formed in the first region from the surface of the hard coat layer to a depth of 100 nm. In this region, there is a first layered region in which the total ratio of Si and O elements is 60% or more, and a second layered region in which the total ratio of Si and O elements is 60% or more. It was confirmed that the layered structure had a second layered region in which the total ratio of the elements was less than 60%. In the hard coat film according to Comparative Example 2, the hard coat layer was formed at a depth of 10 The total element ratio of Si and O was less than 60% throughout the entire region up to 0 nm. Therefore, in the hard coat film according to Comparative Example 2, the hard coat layer is It is confirmed that there is no first layer region in which the total element ratio of Si and O is 60% or more. It was recognized.

[0164] The hard coat films according to Examples 1 to 5 and the functional films according to Examples 6 to 10 were In the film, the Martens hardness of the hard coat layer is explained in the section on the hard coat layer above. When the measurements were performed under the same conditions, the Martens hardness of the hard coat layer was 100MP. It was above a. [Explanation of symbols]

[0165] 10, 20...Functional film 11...Light-transmitting base material 12...Hard coat layer 13...Binder resin 14...Inorganic particles 15...Hard coat film 16...Functional layer 30...Polarizing plate 31...Polarizer 40...Image display device 50...Display panel

Claims

1. A functional film comprising a hard coat layer containing a binder resin and a plurality of inorganic particles, and a functional layer in close contact with a surface of the hard coat layer, the hard coat layer has a layered region in which the density of the inorganic particles is 60% or more in a first region from the surface of the hard coat layer to a depth of 100 nm, and the density of the inorganic particles in a second region in which the density of the inorganic particles is more than 100 nm from the surface of the hard coat layer is 59% or less.

2. The functional film according to claim 1 , wherein at least a portion of the inorganic particles are present at the interface between the hard coat layer and the functional layer, and the inorganic particles are in close contact with the functional layer.

3. 3. The functional film according to claim 1, wherein the hard coat layer has a layered region in the first region where the density of the inorganic particles is 70% or more, and the density of the inorganic particles in the second region is 50% or less.

4. The functional film according to claim 1 , wherein the maximum aggregation degree of the inorganic particles in the second region is 30% or less.

5. The functional film according to claim 1 , wherein the hard coat layer has a thickness of 1 μm or more.

6. The functional film according to claim 1 , further comprising a light-transmitting substrate provided on the side of the hard coat layer opposite to the functional layer side.

7. The functional film according to any one of claims 1 to 6, a polarizer provided on the hard coat layer of the functional film on the opposite side to the functional layer; A polarizing plate comprising:

8. A hard coat film comprising at least a hard coat layer containing a binder resin and a plurality of inorganic particles, the surface of the hard coat layer forms the surface of the hard coat film; the hard coat layer has a portion in which the density of the inorganic particles is 60% or more in a first region extending from the surface of the hard coat layer to a depth of 100 nm, and the density of the inorganic particles in a second region extending from the surface of the hard coat layer to a depth of more than 100 nm is 59% or less.

9. 9. The hard coat film according to claim 8, wherein the inorganic particles contain Si elements, and the hard coat layer comprises, within the first region, a first layered region in which the total element ratio of Si and O is 60% or more, and a second layered region in which the total element ratio of Si and O is less than 60%.

10. 10. The hard coat film according to claim 8, wherein the hard coat layer has a portion in the first region where the density of the inorganic particles is 70% or more, and the density of the inorganic particles in the second region is 50% or less.

11. 11. The hard coat film according to claim 8, wherein the maximum aggregation degree of the inorganic particles in the second region is 30% or less.

12. 12. The hard coat film according to claim 8, wherein the hard coat layer has a thickness of 1 μm or more.

13. The hard coat film according to claim 8 , further comprising a light-transmitting substrate provided on a back surface side of the hard coat layer opposite to the front surface.

14. The hard coat film according to any one of claims 8 to 13, a polarizer provided on one surface of the hard coat film; A polarizing plate comprising:

15. An image display device comprising: the functional film according to claim 1 ; the polarizing plate according to claim 7 or claim 13 ; or the hard coat film according to claim 8 .

Images