Film, method for producing film, polarizing plate, liquid crystal display, and image display device module

Abstract

The present invention provides a film that, even though a cured film is one layer, exhibits excellent scratch resistance in addition to excellent transparency and excellent antiglare properties. This film has a transparent substrate and a cured film provided on the surface of the transparent substrate, wherein: the cured film is a cured product of a curable composition; the curable composition contains at least a difunctional (meth)acrylate and a trifunctional or higher functional (meth)acrylate; the proportion of the trifunctional or higher functional (meth)acrylate is at least 50 mass% with reference to the total mass of non-volatile components in the curable composition; an irregular wrinkle-shaped uneven structure is formed on the surface of the cured film; the root-mean-square gradient Sdq of the coating film surface is less than 0.3; the developed interfacial area ratio Sdr of the coating film surface is not more than 3.0%; and the haze of the film is not more than 60%.

Description

Film, method for manufacturing film, polarizing plate, liquid crystal display, and image display device module

[0001] The present invention relates to a film, a method for manufacturing a film, a polarizing plate, a liquid crystal display, and an image display module. This application claims priority based on Japanese Patent Application No. 2024-158570, filed in Japan on September 12, 2024, the contents of which are incorporated herein by reference.

[0002] Image display devices, such as liquid crystal display devices, organic EL display devices, and touch panels for car navigation systems and smartphones, may have anti-glare films placed on their surfaces to prevent reflections of ambient light onto the screen. In image display devices, anti-glare and anti-reflective properties are required to ensure clear visibility of the display screen by reducing the effects of reflections of ambient light. In particular, image display devices intended for outdoor use, such as automotive image display devices and smartphones, require anti-glare and anti-reflective properties that allow the display screen to be clearly visible even when exposed to strong ambient light such as sunlight.

[0003] In recent years, image display devices have been increasingly used in automotive instrument cluster panels and other applications. Image display devices are being incorporated into a wide variety of equipment, including those used outdoors. Furthermore, with the increasing resolution of image display devices, applying conventional anti-glare films to their surfaces can exaggerate variations in image brightness, resulting in glare and degraded image quality. Suppressing such glare is also becoming increasingly important. Against this backdrop, there is a growing demand for enhancing the anti-glare and anti-reflective properties of image display devices through the use of anti-glare films and other similar technologies.

[0004] Incidentally, molded products used outdoors sometimes require transparency depending on the application. Furthermore, in addition to transparency, anti-glare properties are sometimes desirable. Using an anti-glare film is an effective way to enhance anti-glare properties. However, if extremely high anti-glare properties are imparted to an outdoor molded product using an anti-glare film, there is a risk that the transparency required for outdoor applications may decrease.

[0005] Several anti-glare films have been proposed that can impart anti-glare and anti-reflective properties to image display devices (for example, Patent Documents 1 and 2).

[0006] Patent Document 1 discloses an optical laminate that can be used as an anti-glare film. The optical laminate of Patent Document 1 has a resin layer containing a binder resin and organic particles on at least one surface of a transparent substrate. In the optical laminate of Patent Document 1, the number of organic particles contained in a 0.1 mm × 0.1 mm area when the resin layer is observed from above is 20 or more.

[0007] Patent Document 2 discloses a surface micro-textured body that can be used as an anti-glare film. In the surface micro-textured body of Patent Document 2, the micro-textured areas meander non-parallel to each other and consist of a plurality of irregularly formed convex portions and concave portions between the plurality of convex portions, and have a wavy textured pattern with a most frequent pitch of 3 to 20 μm, and a plurality of concave or convex portions formed on the wavy textured pattern with an apparent most frequent diameter of 1 to 10 μm. Patent Document 2 also discloses a method of forming a textured pattern on the surface of a hard layer by shrinking a heat-shrinkable film to deform the hard layer so that it folds and becomes textured.

[0008] Japanese Patent Publication No. 2020-95092 Japanese Patent Publication No. 2014-206728

[0009] While conventional anti-glare films, including those disclosed in Patent Documents 1 and 2, are thought to exhibit a certain degree of good anti-glare and anti-reflective properties, there is room for further improvement in the performance of anti-glare films, including their anti-glare and anti-reflective properties, for the following reasons.

[0010] For example, in the case of Patent Document 1, although a certain degree of matte finish can be maintained, it is disadvantageous in terms of productivity because it is necessary to provide two layers, an anti-glare layer and a hard layer. Furthermore, because the thickness of the two layers is secured, a thick laminate is obtained, and a thin laminate cannot be obtained.

[0011] The technique described in Patent Document 2 presents difficulties in forming fine irregularities with a pitch of 20 μm or less. In addition, because the angle of inclination of the irregularities tends to be high, there is a risk that the irregularities will be worn away by physical stress applied at an angle. Moreover, due to the material of the surface, the irregularities are easily worn away. For these reasons, it is difficult to use this technique on the outermost surface of image display devices and the like.

[0012] The present invention provides a film that exhibits excellent transparency and excellent anti-glare properties, as well as excellent scratch resistance, even with only one layer of cured film; a method for manufacturing the film; a polarizing plate equipped with the film; a liquid crystal display; and an image display device.

[0013] The present invention has the following aspects: [1] A film comprising a transparent substrate and a cured film provided on the surface of the transparent substrate, wherein the cured film is a cured product of a curable composition, the curable composition contains at least a difunctional (meth)acrylate and a trifunctional or more (meth)acrylate, the proportion of the trifunctional or more (meth)acrylate is 50% by mass or more with respect to the total mass of nonvolatile matter of the curable composition, an irregular wrinkle-like uneven structure is formed on the surface of the cured film, the root mean square gradient Sdq of the coating surface of the irregular wrinkle-like uneven structure as defined in ISO 25178 is less than 0.3, the unfolded interface area ratio Sdr of the coating surface of the irregular wrinkle-like uneven structure as defined in ISO 25178 is 3.0% or less, and the haze is 60% or less. [2] A film comprising a transparent substrate and a cured film provided on the surface of the transparent substrate, wherein the cured film is a cured product of a curable composition, an irregular wrinkle-like uneven structure is formed on the surface of the cured film, the root mean square gradient Sdq of the coating surface of the irregular wrinkle-like uneven structure as defined in ISO 25178 is less than 0.3, the unfolded interface area ratio Sdr of the coating surface of the irregular wrinkle-like uneven structure as defined in ISO 25178 is 3.0% or less, the maximum distance Sz from the highest point to the lowest point of the uneven surface of the irregular wrinkle-like uneven structure as defined in ISO 25178 is 6.0 μm or less, and the haze is 60% or less. [3] A film having a transparent substrate and a cured film provided on the surface of the transparent substrate, wherein the cured film is a cured product of a curable composition, the curable composition contains a difunctional (meth)acrylate, a 3- to 6functional (meth)acrylate, and a heptafunctional (meth)acrylate, the proportion of the heptafunctional (meth)acrylate is 50% by mass or more with respect to the total mass of nonvolatile matter of the curable composition, and an irregular wrinkle-like uneven structure is formed on the surface of the cured film. [4] The film according to any one of [1] to [3], wherein the cured product is a cured product obtained by curing the curable composition by irradiation with vacuum ultraviolet light.[5] The film according to any one of [1] to [4], wherein the curable composition may further contain particles, and the proportion of the particles is 0 to 30% by mass with respect to the total mass of the nonvolatile content of the curable composition. [6] The film according to [5], wherein the average particle diameter of the particles is 0.01 to 30 μm. [7] The film according to [3], wherein the haze is 60% or less. [8] The film according to any one of [1] to [7], wherein the 60° gloss of the surface of the cured film is 10 or more. [9] The film according to [3], wherein the root mean square gradient Sdq of the coating surface defined by ISO 25178 for the irregular wrinkle-like uneven structure is less than 0.3.

[10] The film according to [3], wherein the unfolded interface area ratio Sdr of the coating surface defined by ISO 25178 for the irregular wrinkle-like uneven structure is 3.0% or less.

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

[10] , wherein the Scale area fractal complexity (Safc) of the irregular wrinkled uneven structure as defined in ISO 25178 is 5.0 or less.

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

[11] , wherein the arithmetic mean roughness Ra of the roughness curve element according to JIS B0601:2013 of the irregular wrinkled uneven structure is 1.0 μm or less.

[13] The film according to any one of [1] to

[12] , wherein the inclination angle θα of the roughness curve element according to JIS B0601:2013 of the irregular wrinkled uneven structure is 6.0° or less.

[14] The film according to any one of [1], [3] to

[13] , wherein the maximum distance Sz from the highest point to the lowest point of the uneven surface defined in ISO 25178 for the irregular wrinkle-like uneven structure is 6.0 μm or less.

[15] The film according to any one of [1] to

[14] , wherein the transparent substrate is at least one selected from the group consisting of cycloolefin polymer film, polyethylene terephthalate film, polyacrylic polymer film, and triacetylcellulose film.

[16] A polarizing plate having the film according to any one of [1] to

[15] .

[17] A liquid crystal display having the film according to any one of [1] to

[15] .

[18] An image display module comprising an image display device and a protective member, wherein the protective member is a film according to any one of [1] to

[15] , and the image display device is disposed on the transparent substrate side.

[19] A method for manufacturing a film using a curable composition, wherein the curable composition contains at least a difunctional (meth)acrylate and a trifunctional or more (meth)acrylate, the proportion of the trifunctional or more (meth)acrylate is 50% by mass or more with respect to the total mass of the nonvolatile content of the curable composition, and the method for manufacturing a film comprising applying the curable composition to a transparent substrate and then curing the curable composition by irradiating it with vacuum ultraviolet light.

[20] A method for producing a film using a curable composition, wherein the curable composition contains a difunctional (meth)acrylate, a 3- to 6-functional (meth)acrylate, and a 7- or more functional (meth)acrylate, the proportion of the 7- or more functional (meth)acrylate is 50% by mass or more with respect to the total mass of nonvolatile matter of the curable composition, and the curable composition is cured by applying the curable composition to a transparent substrate and then irradiating it with vacuum ultraviolet light.

[21] A curable composition containing a difunctional (meth)acrylate, a 3- to 6-functional (meth)acrylate, and a 7- or more functional (meth)acrylate, wherein the proportion of the 7- or more functional (meth)acrylate is 50% by mass or more with respect to the total mass of nonvolatile matter of the curable composition.

[0014] According to the present invention, a film is provided that exhibits excellent transparency and excellent anti-glare properties, as well as excellent scratch resistance, even with only one layer of cured film; a method for manufacturing the film; a polarizing plate equipped with the film; a liquid crystal display; and an image display device.

[0015] Figure 1 is a schematic cross-sectional view showing an example of a film. Figure 2 shows an example of an irregular, wrinkled, uneven structure.

[0016] In this specification, the following terms have the meanings set forth below: "(meth)acrylate" is a general term for acrylate and methacrylate. "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group. "(meth)acrylic" is a general term for acrylic and methacrylic. The "~" indicating a numerical range means that the numbers listed before and after it are included as the lower and upper limits. The numerical ranges disclosed herein may be combined in any way to form new numerical ranges.

[0017] Several embodiments will be described below with reference to the drawings. However, the following description concerns representative examples, and the present invention is not limited to those described below. The dimensional ratios in the drawings are for illustrative purposes only and may differ from those of the actual dimensions.

[0018] [Film] Figure 1 shows an example of a film according to the present invention. The film 1 illustrated in Figure 1 has a transparent substrate 3 and a cured film 2 provided on the surface of the transparent substrate 3. In Figure 1, although not shown, an irregular wrinkle-like uneven structure is formed on the surface 2a of the cured film 2.

[0019] An irregular, wrinkled, uneven structure is sometimes commonly referred to as a wrinkle structure. This irregular, wrinkled, uneven structure is a wave-like uneven structure obtained by buckling of the surface layer, and is formed by wrinkles consisting of multiple linear protrusions or depressions that meander in random directions and do not have a specific pattern, regularity, or periodicity when viewed from the thickness direction, such as the labyrinthine structure shown in Figure 2.

[0020] 1. First Embodiment (Cured Film) The cured film of the film according to the first embodiment is a cured product of a curable composition. The curable composition used in the first embodiment contains at least a difunctional (meth)acrylate and a trifunctional or higher (meth)acrylate. Furthermore, it is preferable that the trifunctional or higher (meth)acrylate contains at least a 3- to 6functional (meth)acrylate and a heptafunctional or higher (meth)acrylate.

[0021] Difunctional (meth)acrylates: Difunctional (meth)acrylates are (meth)acrylates that have two polymerizable double bonds, for example, two (meth)acryloyl groups, in one molecule. Examples of difunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, and pentaerythritol di(meth)acrylate. Tomonostearate, glycidyl ether di(meth)acrylate, caprolactone-modified di(meth)acrylate, ethylene oxide-modified di(meth)acrylate, isocyanurate ethylene oxide-modified di(meth)acrylate, propylene oxide-modified di(meth)acrylate, epoxy di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol A alkylene oxide-modified di(meth)acrylate, hydrogenated bisphenol A caprolactone-modified di(meth)acrylate ) Acrylate, Hydrogenated Bisphenol A Glycidyl Ether Modified Di(meth)acrylate, Hydrogenated Bisphenol F Di(meth)acrylate, Hydrogenated Bisphenol F Caprolactone Modified Di(meth)acrylate, Hydrogenated Bisphenol F Alkylene Oxide Modified Di(meth)acrylate, Hydrogenated Bisphenol F Glycidyl Ether Modified Di(meth)acrylate, Bisphenol A Di(meth)acrylate, Bisphenol A Alkylene Oxide Modified Di(meth)acrylate, Bisphenol A Caprolactone Lactone-modified di(meth)acrylate, bisphenol A glycidyl ether-modified di(meth)acrylate, bisphenol F di(meth)acrylate, bisphenol F caprolactone-modified di(meth)acrylate, bisphenol F alkylene oxide-modified di(meth)acrylate, bisphenol F glycidyl ether-modified di(meth)acrylate, fluorenol (meth)acrylate, fluorene alkylene oxide-modified di(meth)acrylate, isobornyl di(meth)acrylate,Examples include tricyclodecanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, adamantyl di(meth)acrylate, dioxaneglycol di(meth)acrylate, isosorbide di(meth)acrylate, and isosorbide alkylene oxide-modified di(meth)acrylate. Among these, structures with unbranched alcohol residues are preferred due to the ease of forming a textured structure. Alkanediol di(meth)acrylate and alkylene oxide-modified di(meth)acrylate are more preferred, and alkyldiol di(meth)acrylates with 4 to 18 carbon atoms are even more preferred. Considering the refractive index required for optical evaluation in display applications, acrylates containing aromatic rings are preferred, and acrylates having the chemical structure of fluorene or bisphenol are even more preferred. However, difunctional (meth)acrylates are not limited to these examples. Difunctional (meth)acrylates may be used individually or in combination of two or more.

[0022] As the difunctional (meth)acrylate, alkyl-modified (meth)acrylate, caprolactone-modified (meth)acrylate, ethylene oxide-modified (meth)acrylate, or propylene oxide-modified (meth)acrylate of the above-mentioned compounds may be used.

[0023] The concentration of double bond groups in the difunctional (meth)acrylate is preferably 0.5 to 15 mmol / g, more preferably 1.0 to 13 mmol / g, even more preferably 1.5 to 12 mmol / g, and particularly preferably 2.0 to 10 mmol / g. When the concentration of double bond groups in the difunctional (meth)acrylate is within the above numerical range, it is easy to achieve both scratch resistance and durability of the cured film and ease of forming surface irregularities.

[0024] Trifunctional or hexafunctional (meth)acrylates: Trifunctional or hexafunctional (meth)acrylates are (meth)acrylates having three or more polymerizable double bonds, for example, three or more (meth)acryloyl groups, in a single molecule. Examples of trifunctional or hexafunctional (meth)acrylates include dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol ethoxytetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, and dimethylolpropane tetra(meth)acrylate, among others. In addition, tripentaerythritol poly(meth)acrylate, acrylic (meth)acrylate with (meth)acrylate introduced into the side chains or terminals of acrylic resin, etc., can also be used. Among these, (meth)acrylate with 7 or more functions can also be used. However, (meth)acrylate with 3 or more functions is not limited to these examples. A single (meth)acrylate with 3 or more functions may be used, or two or more may be used in combination.

[0025] As trifunctional or more (meth)acrylates, alkyl-modified (meth)acrylates, caprolactone-modified (meth)acrylates, ethylene oxide-modified (meth)acrylates, and propylene oxide-modified (meth)acrylates of the above-mentioned compounds may be used. In addition, (meth)acrylates of aliphatic polyols and dendritic aliphatic compounds having acrylate groups at their terminals, known as dendrimers or hyperbranched polymers, are also useful. Commercially available dendritic aliphatic compounds having acrylate groups at their terminals include Viscoat V#1000, V#5020, and STAR-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

[0026] The concentration of double bond groups in the trifunctional or more (meth)acrylate is preferably 2.0 to 16 mmol / g, more preferably 3.0 to 15 mmol / g, even more preferably 4.0 to 14 mmol / g, and particularly preferably 5.0 to 12 mmol / g. When the concentration of double bond groups in the trifunctional or more (meth)acrylate is within the above numerical range, the scratch resistance and durability of the cured film are improved.

[0027] The concentration of double bond groups in the 3-6 functional (meth)acrylate is preferably 2.0-16 mmol / g, more preferably 3.0-15 mmol / g, even more preferably 5.0-14 mmol / g, and particularly preferably 6.0-12 mmol / g. When the concentration of double bond groups in the 3-6 functional (meth)acrylate is within the above numerical range, the scratch resistance and durability of the cured film are improved.

[0028] The concentration of double bond groups in the hepta- or more functional (meth)acrylate is preferably 2.0 to 16 mmol / g, more preferably 2.5 to 15 mmol / g, even more preferably 3.0 to 14 mmol / g, and particularly preferably 4.0 to 12 mmol / g. When the concentration of double bond groups in the hepta- or more functional (meth)acrylate is within the above numerical range, the scratch resistance and durability of the cured film are improved.

[0029] Urethane (meth)acrylate: The curable composition according to the first embodiment may contain urethane (meth)acrylate. Urethane (meth)acrylate is a compound having a (meth)acryloyl group and a urethane bond in one molecule. A difunctional urethane (meth)acrylate having two (meth)acryloyl groups is classified as a difunctional (meth)acrylate. A trifunctional or more urethane (meth)acrylate having three or more (meth)acryloyl groups is classified as a trifunctional or more (meth)acrylate.

[0030] As the urethane (meth)acrylate, a urethane (meth)acrylate having two or more urethane bonds and two or more (meth)acryloyl groups in one molecule is preferred. A urethane (meth)acrylate with seven or more functionalities can also be used. As the urethane (meth)acrylate, for example, the following urethane (meth)acrylate (X) is preferred.

[0031] Urethane (meth)acrylate (X): A reaction product of a hydroxyl group-containing (meth)acrylate (x1), a polyisocyanate (x2), and a polyol (x3) having two or more hydroxyl groups in one molecule.

[0032] The hydroxyl group-containing (meth)acrylate (x1) is not particularly limited as long as it is a (meth)acrylate having a hydroxyl group and a (meth)acryloyl group. Examples include 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate (HPA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxybutyl acrylate (HBA), 4-hydroxybutyl acrylate (4-HBA), 2-hydroxybutyl methacrylate (HBMA), a 1 mol adduct of HEA to caprolactone (Praxel® FA1 from Daicel Corporation), a 2 mol adduct of HEA to caprolactone (Praxel FA2D), a 5 mol adduct of HEA to caprolactone (Praxel FA5), a 10 mol adduct of HEA to caprolactone (Praxel FA10L), and compounds whose skeleton is mono or polypentaerythritol.

[0033] Examples of "compounds whose skeleton is mono or polypentaerythritol" include pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. A single hydroxyl group-containing (meth)acrylate (x1) may be used alone, or two or more may be used in combination.

[0034] Among the hydroxy group-containing (meth)acrylates (x1), from the viewpoints of availability, reactivity, solubility in the curable composition, etc., 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, the caprolactone 1 mol adduct of HEA (Placcel FA1) manufactured by Daicel Corporation, and the caprolactone 2 mol adduct of HEA (Placcel FA2D) are preferable, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate are more preferable, and 2-hydroxyethyl acrylate is even more preferable.

[0035] The polyisocyanate (x2) is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups in one molecule. For example, aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), and lysine diisocyanate; alicyclic polyisocyanates such as norbornane diisocyanate (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanatomethyl)-cyclohexane (hydrogenated XDI), and dicyclohexylmethane diisocyanate (hydrogenated MDI); aromatic polyisocyanates such as 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), and triphenylmethane triisocyanate; isocyanurate forms, adduct forms, and biuret forms of these; are mentioned. The polyisocyanate (x2) may be used alone or in combination of two or more.

[0036] From the viewpoint of weather resistance, aliphatic polyisocyanates and alicyclic polyisocyanates are preferred as polyisocyanates (x2), and hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), bis(isocyanate methyl)cyclohexane (hydrogenated XDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), isocyanurate of hexamethylene diisocyanate manufactured by Asahi Kasei Corporation (product name: Duranate TPA-100), adduct of hexamethylene diisocyanate (product name: Duranate P301-75E), biuret of hexamethylene diisocyanate (product name: Duranate 24A-100), and bifunctional type of hexamethylene diisocyanate (product name: Duranate A-201H) are more preferred. In particular, alicyclic polyisocyanates are more preferred from the viewpoint of scratch resistance, and dicyclohexylmethane diisocyanate (hydrogenated MDI) is even more preferred.

[0037] Polyol (x3) is not particularly limited as long as it is a polyol having two or more hydroxyl groups in one molecule. However, polyol (x3) is a compound other than the hydroxyl group-containing (meth)acrylate (x1). Examples of polyol (x3) include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polycaprolactone polyol (polycaprolactone diol, etc.), polytetramethylene ether glycol (PTMG), polycarbonate polyol (polycarbonate diol, etc.), and lactone polyol (4-hydroxy-N-(2-hydroxyethyl)-N-methylbutanamide, etc., obtained by reacting γ-butyrolactone with N-methylethanolamine). In particular, from the viewpoint of weather resistance, polycaprolactone polyol, polycarbonate polyol, and lactone-based polyol are preferred, with polycarbonate polyol being more preferred. Furthermore, from the viewpoint of improving the flexibility of the cured film and making it less prone to cracking, polyoxyethylene glycol, polyoxybutylene glycol, and polytetramethylene ether glycol (PTMG) are preferred, with polytetramethylene ether glycol being more preferred. Polyol (x3) may be used alone or in combination of two or more types.

[0038] As the polyol (x3), commercially available products may be used. Examples of commercially available polycarbonate polyols include Kuraray Polyol C-590, Kuraray Polyol C-770, Kuraray Polyol C-1050, Kuraray Polyol C-1090, Kuraray Polyol C1065N, Kuraray Polyol C-1015N, Kuraray Polyol C-2090, Kuraray Polyol C-3090 manufactured by Kuraray Co., Ltd.; Duranol T-5650E, Duranol T-5650J, Duranol T-5651, Duranol T-5652, Duranol G-4671, Duranol G-4672, Duranol G3450J, Duranol G3452 manufactured by Asahi Kasei Corporation; Venebiol NL1010DB, Venebiol NL2010DB, Venebiol NL3010DB, Venebiol NL1005B, Venebiol NL2005B, Venebiol NL1030B, Venebiol HS0830B, Venebiol HS0840B, Venebiol HS0840H, Venebiol HS0850H manufactured by Mitsubishi Chemical Corporation.

[0039] Examples of commercially available polytetramethylene ether glycols include PTMG250, PTMG650, PTMG1000, PTMG2000, PTMG3000 manufactured by Mitsubishi Chemical Corporation; PTMEG#220, PTMEG#650, PTMEG#1000, PTMEG#1400, PTMEG#2000 manufactured by Mihama Co., Ltd.; PTG-650, PTG-850SN, PTG-3000 manufactured by Hodogaya Chemical Co., Ltd.

[0040] The urethane (meth)acrylate (X) is obtained by reacting a hydroxy group-containing (meth)acrylate (x1), a polyisocyanate (x2), and a polyol (x3). As the reaction conditions, conditions under heating are preferable. For example, the conditions of a reaction temperature of 70°C and a reaction time of 8 hours can be mentioned.

[0041] Preferred urethane (meth)acrylate (X) includes, for example, a reaction product of a polycarbonate polyol, a diisocyanate compound having an alicyclic structure, and a (meth)acrylate monomer having a hydroxyl group; and a reaction product of polytetramethylene ether glycol, 4-hydroxy-N-(2-hydroxyethyl)-N-methylbutanamide, a diisocyanate compound having an alicyclic structure, and a (meth)acrylate monomer having a hydroxyl group.

[0042] The number of functional groups in the urethane (meth)acrylate, i.e., the number of (meth)acryloyl groups, is preferably 2 to 15, more preferably 2 to 10, even more preferably 2 to 6, particularly preferably 2 to 4, and most preferably 2. When the number of functional groups in the urethane (meth)acrylate is within the above numerical range, scratch resistance is improved.

[0043] The double bond group concentration of the urethane (meth)acrylate is preferably 0.1 to 15 mmol / g, more preferably 0.2 to 10 mmol / g, even more preferably 0.3 to 7.0 mmol / g, and particularly preferably 0.4 to 5.0 mmol / g. When the double bond group concentration of the urethane (meth)acrylate is within the above numerical range, the cured film exhibits excellent adhesion and durability to the transparent substrate. Here, the double bond group concentration refers to the concentration of (meth)acryloyl groups and allyl groups in the urethane (meth)acrylate, that is, the amount of (meth)acryloyl groups and allyl groups introduced.

[0044] The urethane (meth)acrylate preferably has polyol-derived structural units with a number average molecular weight of 500 or more, and more preferably has polyol-derived structural units with a number average molecular weight of 500 to 5000. The polyol-derived structural units contribute to the adhesion, flexibility, and handling properties of the cured product due to its viscosity. The urethane (meth)acrylate may further have polyol-derived structural units with a number average molecular weight of less than 500.

[0045] The weight-average molecular weight of the urethane (meth)acrylate is preferably 1,000 or more, more preferably 1,300 or more, and even more preferably 1,500 or more. When the weight-average molecular weight of the urethane (meth)acrylate is above the lower limit, the flexibility and adhesion of the cured product are easily enhanced. The upper limit of the weight-average molecular weight of the urethane (meth)acrylate is not particularly limited, but from the viewpoint of workability due to viscosity, it is preferably 100,000 or less, more preferably 75,000 or less, and even more preferably 50,000 or less. When the weight-average molecular weight of the urethane (meth)acrylate is below the upper limit, it has low viscosity and good handling properties, and the cured product has excellent scratch resistance. The lower and upper limits of the weight-average molecular weight of the urethane (meth)acrylate can be arbitrarily combined. For example, 1,000 to 100,000 is preferred, 1,300 to 75,000 is more preferred, and 1,500 to 50,000 is even more preferred. The weight-average molecular weight (Mw) of urethane (meth)acrylate can be determined using gel permeation chromatography (GPC) as a converted value based on the polystyrene standard.

[0046] On the other hand, because urethane (meth)acrylate has low fluidity, if the mass ratio of urethane (meth)acrylate increases, it becomes less likely for irregularities to form, and the low gloss due to the matte effect may not be achieved.

[0047] Acrylic (meth)acrylate: The acrylic (meth)acrylate refers to an acrylic resin into which (meth)acryloyl groups have been introduced by the following methods. For example, methods for introducing (meth)acryloyl groups include: reacting an acrylic resin having epoxy groups with a compound having (meth)acryloyl groups and carboxyl groups (Method 1); reacting an acrylic resin having carboxyl groups with a compound having (meth)acryloyl groups and epoxy groups (Method 2); reacting an acrylic resin having hydroxyl groups with a compound having (meth)acryloyl groups and carboxyl groups (Method 3); reacting an acrylic resin having carboxyl groups with a compound having (meth)acryloyl groups and hydroxyl groups (Method 4); reacting an acrylic resin having isocyanate groups with a compound having (meth)acryloyl groups and hydroxyl groups (Method 5); and reacting an acrylic resin having hydroxyl groups with a compound having (meth)acryloyl groups and isocyanate groups (Method 6).

[0048] In Method 1 described above, examples of vinyl monomers having epoxy groups used to obtain an acrylic resin having epoxy groups include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Among these, glycidyl (meth)acrylate is particularly preferred, and glycidyl methacrylate is especially preferred, considering its reactivity and ease of use. These may be used individually or in combination of two or more.

[0049] Furthermore, examples of compounds having a (meth)acryloyl group and a carboxyl group in Method 1 include (meth)acrylic acid, carboxyethyl (meth)acrylate, adducts of glycerin di(meth)acrylate and succinic anhydride, adducts of pentaerythritol tri(meth)acrylate and succinic anhydride, and adducts of pentaerythritol tri(meth)acrylate and phthalic anhydride. Among these, (meth)acrylic acid and adducts of pentaerythritol tri(meth)acrylate and succinic anhydride are preferred, (meth)acrylic acid is more preferred, and acrylic acid is even more preferred. Only one compound having a (meth)acryloyl group and a carboxyl group may be used, or two or more may be combined.

[0050] In Method 2 described above, examples of carboxyl-group-containing (meth)acrylates used to obtain an acrylic resin containing carboxyl groups include (meth)acrylic acid, carboxyethyl (meth)acrylate, and polybasic acid-modified (meth)acrylate. Among these, (meth)acrylic acid is preferred, and acrylic acid is more preferred. These may be used individually or in combination of two or more.

[0051] Furthermore, in Method 2, examples of compounds having a (meth)acryloyl group and an epoxy group include glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether. Among these, glycidyl (meth)acrylate is preferred. These may be used individually or in combination of two or more.

[0052] In method 3 described above, examples of hydroxyl-containing (meth)acrylates used to obtain an acrylic resin containing hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and hydroxypropyl (meth)acrylate. These may be used individually or in combination of two or more.

[0053] Furthermore, in method 3, the compound having a (meth)acryloyl group and a carboxyl group can be the same as the compound in method 1.

[0054] In method 4, the acrylic resin having a carboxyl group can be the same as that used in method 2.

[0055] Furthermore, in method 4, examples of compounds having a (meth)acryloyl group and a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and hydroxypropyl (meth)acrylate. These may be used individually or in combination of two or more.

[0056] In the above method 5, examples of vinyl monomers having isocyanate groups used to obtain an acrylic resin having isocyanate groups include isocyanate ethyl (meth)acrylate.

[0057] Furthermore, in method 5, the compound having a (meth)acryloyl group and a hydroxyl group can be, for example, the same compound as that listed in method 4.

[0058] In method 6, the acrylic resin having a hydroxyl group can be the same as the compound used in method 3.

[0059] Furthermore, in method 6, examples of compounds having a (meth)acryloyl group and an isocyanate group include isocyanate ethyl (meth)acrylate. These may be used individually or in combination of two or more.

[0060] Among the above methods, Method 1 is preferred from the viewpoint of ease of controlling the reaction. In Method 1, the (meth)acryloyl group is introduced by a ring-opening and addition reaction between the epoxy group of the acrylic resin having an epoxy group and the carboxyl group in the compound having both a (meth)acryloyl group and a carboxyl group.

[0061] In the above method 1, the proportion of constituent units derived from monomers having epoxy groups in the acrylic resin having epoxy groups is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total mass of constituent units derived from monomers constituting the acrylic resin having epoxy groups. There is no particular upper limit, but 99.9% by mass or less is preferred. By using this range, not only is the adhesion, scratch resistance, and hardness of the cured film to the transparent substrate improved, but the uneven shape tends to become finer, and a decrease in Rsm, a decrease in Ra, and in some cases an increase in haze and a decrease in gloss can be achieved. The lower and upper limits of the proportion of constituent units derived from monomers having epoxy groups can be arbitrarily combined, for example, 5 to 99.9% by mass, 10 to 99.9% by mass, or 15 to 99.9% by mass.

[0062] Furthermore, in Method 1 described above, the compound having (meth)acryloyl groups and carboxyl groups is preferably 10 to 150 mol%, more preferably 30 to 130 mol%, and even more preferably 50 to 110 mol%, in proportion to the epoxy groups in the acrylic resin having epoxy groups. Using this range is preferable from the viewpoint of allowing the reaction to proceed without excess or deficiency and reducing the amount of raw material residue.

[0063] Furthermore, acrylic resins, such as the acrylic resin having the epoxy group described above, may also be copolymers of (meth)acrylates or other vinyl monomers other than those described above. The polymerization reaction of these raw materials is usually radical polymerization and can be carried out under conventionally known conditions.

[0064] Examples of monomers that can be used in combination as raw materials include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, methoxy (poly)ethylene glycol (meth)acrylate, methoxy (poly)propylene glycol (meth)acrylate, methoxy (poly)ethylene glycol (poly)propylene glycol (meth)acrylate, octoxy (poly)ethylene glycol (meth)acrylate, octoxy (poly)propylene glycol (meth)acrylate, Examples include (meth)acrylates such as meth)acrylate, octoxytetramethylene glycol (meth)acrylate, lauroxy(poly)ethylene glycol (meth)acrylate, and stearoxy(poly)ethylene glycol (meth)acrylate; acrylamides such as ethyl (meth)acrylamide, n-butyl (meth)acrylamide, i-butyl (meth)acrylamide, t-butyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, and N,N-dihydroxyethyl (meth)acrylamide; and styrene monomers such as styrene, p-chlorostyrene, and p-bromostyrene. These may be used individually or in combination of two or more.

[0065] Acrylic resins can be produced by radical polymerization using the above-mentioned vinyl monomer raw materials. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

[0066] Examples of organic solvents used in radical polymerization include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; and aromatic hydrocarbon solvents such as toluene. These organic solvents may be used individually or in combination of two or more.

[0067] Examples of radical polymerization initiators used in radical polymerization include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; and azo compounds such as 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used individually or in combination of two or more.

[0068] It is preferable to use a radical polymerization initiator in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the total amount of monomers used as raw materials.

[0069] Furthermore, during radical polymerization, chain transfer agents can be used to control the weight-average molecular weight of the acrylic resin. Examples of chain transfer agents include butanethiol, octanthiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, and 2,2-(ethylenedi Examples of thiol compounds include oxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, 2-mercaptoethyl octanoate, 1,8-dimercapto-3,6-dioxaoctane, decantrithiol, dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccal acid, and 2-mercaptoethanesulfonic acid. These may be used individually or in combination of two or more.

[0070] The amount of chain transfer agent used is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1.0 to 15 parts by mass, per 100 parts by mass of the total amount of monomer raw materials.

[0071] The reaction time for radical polymerization is preferably 1 to 20 hours, and more preferably 3 to 12 hours. The reaction temperature is preferably 40 to 120°C, and more preferably 50 to 100°C.

[0072] To react an acrylic resin with a compound having (meth)acryloyl and carboxyl groups, the compound having (meth)acryloyl and carboxyl groups is added to the acrylic resin obtained as described above, and the reaction is carried out in the presence of one or more catalysts such as triphenylphosphine, tetrabutylammonium bromide, tetramethylammonium chloride, and triethylamine, at a temperature of usually 90 to 140°C, preferably 100 to 120°C, for usually 3 to 9 hours. Here, it is preferable to use the catalyst in a ratio of about 0.5 to 3 parts by mass per 100 parts by mass of the total of the raw material acrylic resin and the compound having (meth)acryloyl and carboxyl groups. This reaction may be carried out immediately after producing the acrylic resin by polymerization, or the acrylic resin may be separated from the reaction system first, and then the compound having (meth)acryloyl and carboxyl groups may be added.

[0073] The double bond group concentration in acrylic (meth)acrylate is preferably in the range of 0.1 to 20 mmol / g, more preferably 0.2 to 15 mmol / g, even more preferably 0.5 to 10 mmol / g, particularly preferably 0.8 to 8.0 mmol / g, and most preferably 1.0 to 5.0 mmol / g. Using this range not only improves the adhesion, scratch resistance, and hardness of the cured film to the transparent substrate, but also tends to refine the uneven surface shape, achieving a decrease in Rsm, a decrease in Ra, and in some cases an increase in haze or a decrease in gloss. The double bond group concentration referred to here means the concentration of (meth)acryloyl groups and allyl groups in acrylic (meth)acrylate, that is, the amount of (meth)acryloyl groups and allyl groups introduced.

[0074] The weight-average molecular weight (Mw) of the acrylic (meth)acrylate should be appropriately selected depending on the application of the curable composition, but is usually 5,000 or more, preferably 7,000 or more, more preferably 9,000 or more, usually 200,000 or less, preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less. Within the above range, surface irregularities are easily formed. The lower and upper limits of the weight-average molecular weight (Mw) of the acrylic (meth)acrylate can be arbitrarily combined, for example, 5,000 to 200,000, 7,000 to 100,000, 9,000 to 70,000, or 9,000 to 50,000. The weight-average molecular weight (Mw) of the acrylic (meth)acrylate can be determined as a converted value using polystyrene standards by gel permeation chromatography (GPC). The specific measurement conditions are shown in the examples below.

[0075] Monofunctional (meth)acrylates: The curable composition may further contain monofunctional (meth)acrylates having one polymerizable double bond, such as a (meth)acryloyl group, in one molecule, from the viewpoint of adjusting viscosity and curing speed. Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl acrylate, hexyl acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cresol (meth)acrylate, dicyclopentenyl (meth)acrylate Examples include acrylates, dicyclopentenyloxyethyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyldiethylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, lauryl (meth)acrylate, polyurethane mono(meth)acrylate, polyepoxy mono(meth)acrylate, polyester mono(meth)acrylate, etc. However, monofunctional (meth)acrylates are not limited to these examples. Monofunctional (meth)acrylates may be used alone or in combination of two or more types.

[0076] The concentration of double bonds in the monofunctional (meth)acrylate is preferably 1.0 to 18 mmol / g, more preferably 1.5 to 17 mmol / g, even more preferably 2.0 to 16 mmol / g, and particularly preferably 3.0 to 15 mmol / g. When the concentration of double bonds in the monofunctional (meth)acrylate is within the above numerical range, the ease with which surface irregularities are formed in the cured film is improved.

[0077] The curable composition may also contain curable compounds other than (meth)acrylates that can be cured by irradiation with vacuum ultraviolet light. Examples include vinyl compounds such as styrene, vinyl halides, and vinyl acetate, and diene compounds such as vinylidene halides, 1,3-butadiene, isoprene, and chloroprene.

[0078] Particles: In addition to bifunctional (meth)acrylates and trifunctional or more (meth)acrylates, the curable composition may further contain particles. The particles may be inorganic particles or organic particles, and are not particularly limited. The particles may be surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group. The organic particles may be crosslinked particles.

[0079] Examples of inorganic particles include aluminum oxide, silica, zirconia, titania, hollow silica particles, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, zirconium oxide, and titanium oxide. However, inorganic particles are not limited to these examples. One type of inorganic particle may be used alone, or two or more types may be used in combination.

[0080] Examples of organic particles include polymethyl methacrylate particles, acrylic-styrene copolymer particles, melamine resin particles, urea resin particles, phenolic resin particles, epoxy resin particles, polycarbonate particles, polystyrene particles, polyvinyl chloride particles, benzoguanamine-melamine-formaldehyde condensate particles, silicone particles, fluororesin particles, and polyester resin particles. However, organic particles are not limited to these examples. Organic particles may be used individually or in combination of two or more types.

[0081] The average particle diameter is preferably 0.01 to 30 μm, more preferably 0.05 to 10 μm, even more preferably 0.1 to 5 μm, and particularly preferably 0.5 to 3 μm. If the average particle diameter is above the lower limit of the above numerical range, a film exhibiting good quality matte finish is more likely to be obtained. If the average particle diameter is below the upper limit of the above numerical range, a film with suppressed haze and improved light transmittance is more likely to be obtained. The average particle diameter is the 50% cumulative value of the volume-based particle size distribution measured using a particle size distribution analyzer.

[0082] Photopolymerization initiator: The curable composition may further contain a photopolymerization initiator. Examples of photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, and p-t-butyldichloro Examples include acetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenylsulfone, and tribromomethylphenylsulfone. However, photopolymerization initiators are not limited to these examples. One photopolymerization initiator may be used alone, or two or more may be used in combination.

[0083] Organic solvents: The curable composition may further contain organic solvents. Examples of organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenethole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; and halogen solvents such as dichloromethane and chloroform. However, organic solvents are not limited to these examples. One organic solvent may be used alone, or two or more may be used in combination.

[0084] Composition of the curable composition: The composition of the curable composition is not particularly limited, provided that the proportion of trifunctional or more (meth)acrylates is 50% by mass or more relative to the total mass of nonvolatile content of the curable composition. In one example, it is preferable that the proportion of heptafunctional or more (meth)acrylates is 50% by mass or more relative to the total mass of nonvolatile content of the curable composition. The nonvolatile content of the curable composition can be measured as the amount of residue when the curable composition is heated at 100°C for 1 hour.

[0085] The proportion of trifunctional or more (meth)acrylate in the curable composition is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 90% by mass, of the total mass of nonvolatile components of the curable composition. When the proportion of trifunctional or more (meth)acrylate is above the lower limit of the above numerical range, a film with improved scratch resistance and durability is more likely to be obtained. When the proportion of trifunctional or more (meth)acrylate is below the upper limit of the above numerical range, a film with good quality unevenness can be formed, and a film with the desired matte finish is more likely to be obtained.

[0086] The proportion of 3-6 functional (meth)acrylates in the curable composition is preferably 5-95% by mass, more preferably 8-80% by mass, and even more preferably 10-60% by mass, based on the total mass of non-volatile components of the curable composition. When the proportion of 3-6 functional (meth)acrylates is above the lower limit of the above numerical range, a film with improved scratch resistance and durability is easily obtained. When the proportion of 3-6 functional (meth)acrylates is below the upper limit of the above numerical range, a film with good quality unevenness can be formed, and a film with the desired matte finish is easily obtained. At the same time, a film with excellent curlability and processability is easily obtained.

[0087] The proportion of heptafunctional (meth)acrylate in the curable composition is preferably 30 to 99% by mass, more preferably 50 to 90% by mass, and even more preferably 60 to 80% by mass, based on the total mass of nonvolatile components of the curable composition. When the proportion of heptafunctional (meth)acrylate is above the lower limit of the above numerical range, a film with improved scratch resistance and durability is easily obtained. When the proportion of heptafunctional (meth)acrylate is below the upper limit of the above numerical range, a film with good quality unevenness can be formed, and a film with the desired matte finish is easily obtained. At the same time, a film with excellent curlability and processability is easily obtained.

[0088] The proportion of difunctional (meth)acrylate in the curable composition is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and even more preferably 10 to 30% by mass, relative to the total mass of nonvolatile components of the curable composition. When the proportion of difunctional (meth)acrylate is above the lower limit of the above numerical range, a film with excellent workability due to low viscosity and suppression of curl due to curing shrinkage is easily obtained. When the proportion of difunctional (meth)acrylate is below the upper limit of the above numerical range, a film with excellent scratch resistance and durability is easily obtained.

[0089] The proportion of monofunctional (meth)acrylate in the curable composition is not particularly limited. It can be appropriately changed considering viscosity and curing speed. For example, the proportion of monofunctional (meth)acrylate in the curable composition may be 0.1 to 50% by mass, 1 to 40% by mass, or 5 to 30% by mass, based on the total mass of nonvolatile matter in the curable composition.

[0090] The proportion of urethane (meth)acrylate in the curable composition is preferably 0 to 95% by mass, more preferably 0 to 90% by mass, and even more preferably 0 to 75% by mass, based on the total mass of nonvolatile components of the curable composition. When the proportion of urethane (meth)acrylate is above the lower limit of the above numerical range, it is easier to obtain a film with excellent processability and easy control of the size of irregularities. When the proportion of urethane (meth)acrylate is below the upper limit of the above numerical range, it is easier to obtain a film with excellent scratch resistance and durability.

[0091] The proportion of acrylic (meth)acrylate in the curable composition is preferably 0 to 95% by mass, more preferably 0 to 90% by mass, and even more preferably 0 to 75% by mass, based on the total mass of non-volatile components of the curable composition. When the proportion of acrylic (meth)acrylate is above the lower limit of the above numerical range, it is easier to obtain a film with excellent processability and easy control of the size of irregularities. When the proportion of acrylic (meth)acrylate is below the upper limit of the above numerical range, it is easier to obtain a film with excellent scratch resistance and durability.

[0092] The proportion of particles in the curable composition is preferably 0 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 1 to 15% by mass, relative to the total mass of nonvolatile components of the curable composition. If the proportion of particles is greater than 0 within the above numerical range, a film with good quality unevenness can be formed, and a film with easily controllable haze and gloss can be obtained. If the proportion of particles is below the upper limit of the above numerical range, a film with excellent scratch resistance and durability can be obtained.

[0093] The proportion of the photopolymerization initiator in the curable composition is not particularly limited. It can be appropriately changed considering the curing rate of each component. For example, the proportion of the photopolymerization initiator in the curable composition may be 0.1 to 20% by mass, 0.5 to 10% by mass, or 1 to 8% by mass, based on the total mass of the nonvolatile content of the curable composition.

[0094] The proportion of organic solvent in the curable composition is not particularly limited. It can be appropriately changed considering viscosity and workability during application. The proportion of organic solvent in the curable composition is preferably 10 to 1900 parts by mass, and more preferably 40 to 400 parts by mass, per 100 parts by mass of the non-volatile content of the curable composition. If the organic solvent content is within the above range, the operability of the curable composition during application will be improved.

[0095] (Transparent Substrate) The transparent substrate is not particularly limited as long as its total light transmittance is 50% or more. For example, various resin substrates such as resin films, polymer boards, and polymer molded products can be used. The resin substrate may be a single layer or a multilayer structure of two or more layers, and is not particularly limited. If necessary, glass or the like can be used as the transparent substrate. The total light transmittance is a value measured in accordance with JIS Z 8722:2009 (Method of measurement of transparent objects: Geometric conditions for irradiation and reception) and JIS K 7361-1:1997 (Plastics - Test method for total light transmittance of transparent materials).

[0096] Examples of resin films include triacetylcellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic polymer film, polyurethane polymer film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth)acrylonitrile film, cycloolefin polymer (COP) film, stretched polypropylene film, and unstretched polypropylene film. As a transparent substrate, at least one selected from the group consisting of COP film, PET film, polyacrylic polymer film, and TAC film is preferred from the viewpoint of minimizing phase difference. In the case of PET film, it is preferable to have a zero retardation film with an in-plane retardation of 100 nm or less, particularly 50 nm or less, or a high retardation film with an in-plane retardation of 3000 nm to 30000 nm.

[0097] Examples of polymer sheets and polymer molded articles include acrylic sheets, triacetylcellulose sheets, polyethylene terephthalate sheets, diacetylene cellulose sheets, acetate butyrate cellulose sheets, polyethersulfone sheets, polyurethane sheets, polycarbonate sheets, polysulfone sheets, polyether sheets, polymethylpentene sheets, polyetherketone sheets, (meth)acrylonitrile sheets, and the like.

[0098] The thickness of the transparent substrate can be selected as appropriate depending on the application. The thickness of the transparent substrate may be approximately 2 to 10,000 μm, approximately 5 to 1,000 μm, or approximately 10 to 250 μm.

[0099] (Film properties) The arithmetic mean roughness Ra of the roughness curve elements according to JIS B0601:2013, which have an irregular wrinkle-like uneven structure, is preferably 1.0 μm or less, more preferably 0.8 μm or less, and even more preferably 0.7 μm or less. When the arithmetic mean roughness Ra is below the above upper limit, a film with improved scratch resistance is easily obtained. The lower limit of the average roughness Ra is not particularly limited, but from the viewpoint of mattiness, it may be, for example, 0.1 μm, 0.2 μm, or 0.3 μm. The lower and upper limits of the average roughness Ra can be arbitrarily combined, for example, 0.1 to 1.0 μm, 0.2 to 0.8 μm, or 0.3 to 0.7 μm.

[0100] The average length Rsm of the roughness curve elements conforming to JIS B0601:2013, which have an irregular wrinkle-like uneven structure, is preferably 30 μm or more, more preferably 33 μm or more, and even more preferably 37 μm or more. When the average length Rsm is above the lower limit, it is easier to achieve the desired matte finish, and at the same time, the unevenness is less likely to be abraded, so it is easier to obtain a film with improved scratch resistance. The upper limit of the average length Rsm is not particularly limited, but for example it may be 200 μm, 150 μm, or 100 μm. The lower and upper limits of the average length Rsm can be arbitrarily combined, for example it can be 30 to 200 μm, 33 to 150 μm, or 37 to 100 μm.

[0101] The inclination angle θα of the roughness curve element conforming to JIS B0601:2013, which has an irregular wrinkle-like uneven structure, is preferably 6.0° or less, more preferably 5.5° or less, and even more preferably 5.0° or less. When the inclination angle θα is below the upper limit, a film with improved scratch resistance is easily obtained. The lower limit of the inclination angle θα is not particularly limited, but from the viewpoint of mattiness, it may be, for example, 1.0°, 1.5°, or 2.0°. The lower and upper limits of the inclination angle θα can be arbitrarily combined, for example, 1.0 to 6.0°, 1.5 to 5.5°, or 2.0 to 5.0°.

[0102] The haze of the film is 60% or less, preferably 55% or less, and more preferably 50% or less. When the haze of the film is below the upper limit, it is easier to obtain a film with improved matte finish. The lower limit of the haze of the film is not particularly limited, but from the viewpoint of transparency and visibility, it may be, for example, 4.0%, 6.0%, or 8.0%. The lower and upper limits of the haze of the film can be arbitrarily combined, for example, 4.0 to 60%, 6.0 to 55%, or 8.0 to 50%.

[0103] The 60° gloss of the surface of the cured film is preferably 10 or higher, more preferably 15 or higher, and even more preferably 20 or higher. When the 60° gloss of the surface of the cured film is above the lower limit, a film that easily achieves the desired matte and gloss properties can be obtained. The upper limit of the 60° gloss of the surface of the cured film is not particularly limited, but may be 50, 45, or 40, for example. The lower and upper limits of the 60° gloss of the surface of the cured film can be arbitrarily combined, for example, 10 to 50, 15 to 45, or 20 to 40.

[0104] The 20° gloss of the surface of the cured film is preferably 3.0 or higher, more preferably 5.0 or higher, and even more preferably 6.0 or higher. When the 20° gloss of the surface of the cured film is above the lower limit, a film that easily achieves the desired matte finish and low gloss can be obtained. The upper limit of the 20° gloss of the surface of the cured film is not particularly limited, but may be 30, 25, or 20, for example. The lower and upper limits of the 20° gloss of the surface of the cured film can be arbitrarily combined, for example, 3.0 to 30, 5.0 to 25, or 6.0 to 20.

[0105] The Scale area fractal complexity (Safc), as defined in ISO 25178 for the irregular wrinkle-like uneven structure, is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. When Safc is below the upper limit, there are fewer surfaces with sharp irregularities, resulting in a film that easily achieves good scratch resistance and desired matte and gloss properties. The lower limit of Safc is not particularly limited, but may be, for example, 0.1, 0.5, or 1.0. The lower and upper limits of Safc can be arbitrarily combined, for example, 0.1 to 5.0, 0.5 to 4.0, or 1.0 to 3.0.

[0106] The root mean square gradient Sdq of the coating surface defined in ISO 25178 for an irregular wrinkle-like uneven structure is less than 0.30, preferably 0.25 or less, and more preferably 0.20 or less. When the root mean square gradient Sdq is below the upper limit, local gradients are reduced, and a film with good scratch resistance and desirable matte and gloss properties can be obtained. The lower limit of the root mean square gradient Sdq is not particularly limited, but may be, for example, 0.01, 0.05, or 0.10. The lower and upper limits of the root mean square gradient Sdq can be arbitrarily combined, for example, 0.01 or more and less than 0.30, 0.05 to 0.25, or 0.10 to 0.20.

[0107] The unfolded interface area ratio Sdr of the coating surface defined in ISO 25178 for an irregular wrinkle-like uneven structure is 3.0% or less, preferably 2.5% or less, and more preferably 2.0% or less. When the unfolded interface area ratio Sdr is below the upper limit, the uneven surface area is reduced, and a film is obtained that easily achieves good scratch resistance and desired matte and gloss properties. The lower limit of the unfolded interface area ratio Sdr is not particularly limited, but may be, for example, 0.1, 0.3, or 0.5. The lower and upper limits of the unfolded interface area ratio Sdr can be arbitrarily combined, for example, 0.1 to 3.0%, 0.3 to 2.5%, or 0.5 to 2.0%.

[0108] The maximum distance Sz from the highest point to the lowest point of the uneven surface, as defined in ISO 25178, which has an irregular wrinkle-like uneven structure, is preferably 6.0 μm or less, more preferably 5.5 μm or less, and even more preferably 5.0 μm or less. When the maximum distance Sz is below the upper limit, extremely high unevenness is reduced, and a film is obtained that easily achieves good scratch resistance and the desired matte and gloss properties. The lower limit of the maximum distance Sz is not particularly limited, but may be, for example, 0.1 μm, 1.0 μm, or 2.0 μm. The lower and upper limits of the maximum distance Sz can be arbitrarily combined, for example, 0.1 to 6.0 μm, 1.0 to 5.5 μm, or 2.0 to 5.0 μm.

[0109] (Method for manufacturing the film) The film is obtained by applying a curable composition to a transparent substrate, removing the solvent by hot air drying as needed, and then irradiating it with vacuum ultraviolet light. When the curable composition hardens, the surface of the hardened film hardens first, forming a hardened film. Then, due to the shrinkage stress when the interior of the hardened film hardens, the hardened film on the surface shrinks, resulting in the appearance of an irregular wrinkle-like uneven structure on the surface of the hardened film.

[0110] Irregular wrinkled, uneven structures can be obtained by increasing the irradiation intensity of vacuum ultraviolet light and shortening the curing time of the curable composition to obtain smaller wrinkled structures, and by decreasing the irradiation intensity of vacuum ultraviolet light and lengthening the curing time of the curable composition to obtain larger wrinkled structures.

[0111] Irregular wrinkled surface can be made smaller by increasing the viscosity of the curable composition (excluding the solvent) and reducing its fluidity. Conversely, a larger irregular wrinkled surface can be made by decreasing the viscosity of the curable composition (excluding the organic solvent) and improving its fluidity.

[0112] Suitable atmospheres for curing curable compositions include air, nitrogen, carbon dioxide, and argon. From the viewpoint of practicality and economy, air, nitrogen, and carbon dioxide are preferred. Furthermore, it is preferable to perform the vacuum ultraviolet irradiation in an environment with low oxygen levels, such as a nitrogen atmosphere. The oxygen concentration in the atmosphere is preferably in the range of 10% or less, more preferably 5.0% or less, even more preferably 3.0% or less, and particularly preferably 1.0% or less.

[0113] Vacuum ultraviolet light is ultraviolet light with a wavelength of 200 nm or less, and among these, excimer light with a half-width of 50 nm or less is optimal. Examples of excimer light include argon (126 nm), krypton (146 nm), xenon (172 nm), and argon-fluorine (193 nm). Among these, xenon excimer light is preferred considering ease of handling, the ability to form an effective uneven structure in the cured film, and the curability of the curable composition.

[0114] The cumulative amount of vacuum ultraviolet light irradiated is preferably 1 to 5000 mJ / cm². ２ More preferably, 2 to 3000 mJ / cm² ２ More preferably 3 to 1000 mJ / cm² ２ Particularly preferably 5 to 500 mJ / cm² ２ The range is as follows. Furthermore, the illuminance is preferably 1 to 1000 mW / cm². ２ More preferably 5 to 500 mW / cm² ２ More preferably 10 to 300 mW / cm² ２ It is within the range.

[0115] After irradiating with vacuum ultraviolet light, it is preferable to irradiate with active energy rays other than vacuum ultraviolet light to cure the hardened film to its depths. Examples of active energy rays include ultraviolet light and electron beams. Considering the curability of the hardened film, ultraviolet light is preferred. Examples of ultraviolet light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electrodeless UV lamps using magnetrons, and LEDs.

[0116] When using ultraviolet light, preferable curing conditions are, for example, using a high-pressure mercury lamp, and the integrated light quantity of ultraviolet light with a wavelength of 340 to 380 nm is preferably 1 to 5000 mJ / cm ２ , more preferably 50 to 3000 mJ / cm ２ , even more preferably is 100 to 2000 mJ / cm ２ , particularly preferably 200 to 1000 mJ / cm ２ within the range. Also, as the illuminance, it is preferably 1 to 1000 mW / cm ２ , more preferably 50 to 500 mW / cm ２ , even more preferably 80 to 300 mW / cm ２ within the range.

[0117] (Primer layer) There may be a primer layer between the transparent substrate and the cured film. The primer layer is a layer for imparting various functions such as improving adhesion. The primer layer may have a plurality of functions in one layer or may be composed of a plurality of layers.

[0118] In a preferable aspect, the primer layer is an adhesion improvement layer. If the adhesion between the transparent substrate and the cured film is insufficient, the laminate may not be usable depending on the application. By having an adhesion improvement layer, the adhesion between the transparent substrate and the cured film is improved, and the laminate can be used for various applications. From the viewpoint of improving adhesion and the like, it is preferable that the adhesion improvement layer contains either or both of a resin and a compound derived from a crosslinking agent.

[0119] As the resin contained in the primer layer, conventionally known resins can be used. Specific examples of the resin include polyester resin, acrylic resin, urethane resin, polyvinyl resin (such as polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.). Among them, considering the adhesion performance and coating property, polyester resin, acrylic resin, and urethane resin are preferable.

[0120] When the transparent substrate is a resin film, from the viewpoint of affinity with the transparent substrate, it is preferable that the resin contained in the primer layer is the same type of resin as the resin film. For example, when the transparent substrate is a polyester film, it is preferable that the primer layer contains polyester resin. When the transparent substrate is a poly(meth)acrylate film, it is preferable that the primer layer contains acrylic resin.

[0121] Polyester resins include those whose main components are polycarboxylic acids and polyhydroxy compounds. Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfisoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, monopotassium salt of trimellitic acid, and their ester-forming derivatives. Examples of polyvalent hydroxy compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, and potassium dimethylolpropionate. From these compounds, one or more can be appropriately selected, and a polyester resin can be synthesized by a conventional polycondensation reaction.

[0122] Acrylic resin is a polymer of polymerizable monomers, including (meth)acrylic monomers. Examples of acrylic resins include homopolymers and copolymers of (meth)acrylic monomers, and copolymers of (meth)acrylic monomers and polymerizable monomers other than (meth)acrylic monomers.

[0123] Acrylic resins may also be copolymers of these polymers with other polymers (e.g., polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers and graft copolymers. This also includes polymers (and possibly mixtures of polymers) obtained by polymerizing polymerizable monomers in a solution or dispersion of polyester. Similarly, it includes polymers (and possibly mixtures of polymers) obtained by polymerizing polymerizable monomers in a solution or dispersion of polyurethane. Similarly, it also includes polymers (and possibly mixtures of polymers) obtained by polymerizing polymerizable monomers in a solution or dispersion of other polymers.

[0124] The polymerizable monomers mentioned above are not particularly limited, but some representative compounds include, for example, carboxyl group-containing monomers and their salts such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, monobutyl hydroxyl fumarate, and monobutyl hydroxyitaconate; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethyl Examples include alkyl(meth)acrylates such as hexyl(meth)acrylate and lauryl(meth)acrylate; nitrogen-containing monomers such as (meth)acrylamide, diacetone acrylamide, N-methylolacrylamide, and (meth)acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene; vinyl esters such as vinyl propionate and vinyl acetate; silicon-containing monomers such as γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and pyridene chloride; and conjugated dienes such as butadiene.

[0125] Urethane resin is a polymer compound that contains urethane bonds within its molecule, and is typically synthesized by the reaction of a polyol with a polyisocyanate compound. Chain extenders may be used when synthesizing urethane resin. Examples of polyols used to obtain urethane resin include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols. These compounds may be used individually or in combination of two or more.

[0126] Polycarbonate polyols are obtained by the reaction (de-alcoholization reaction) of a polyhydric alcohol with a carbonate compound. Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylolheptane. Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Examples of polycarbonate polyols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate.

[0127] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol.

[0128] Examples of polyester polyols include those obtained by the reaction of a polyhydric carboxylic acid or its acid anhydride with a polyhydric alcohol, and those having derivative units of lactone compounds such as polycaprolactone. Examples of polyhydric carboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, and isophthalic acid. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, and 2-methyl-2-propyl-1,3-propanediol. Examples include 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyldialkanolamines, and lactonediols.

[0129] Considering adhesion performance, polyester polyols and polycarbonate polyols are preferred as polyols, with polyester polyols being particularly preferred.

[0130] Examples of polyisocyanate compounds used to obtain urethane resins include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylenediphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates having aromatic rings such as α,α,α',α'-tetramethylxylylene diisocyanate; aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and isopropylidene dicyclohexyl diisocyanate. These may be used individually or in combination of two or more.

[0131] There are no particular restrictions on the chain extender as long as it has two or more active groups that react with isocyanate groups, and generally, chain extenders having two hydroxyl groups or amino groups can be mainly used. Examples of chain extenders having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol, and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and ester glycols such as neopentyl glycol hydroxypivalate, and other glycol compounds. Examples of chain extenders having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine, and diphenylmethanediamine; aliphatic diamines such as ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine; and alicyclic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylthincyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, and 1,3-bisaminomethylcyclohexane.

[0132] Urethane resins are typically used in the form of dispersions or solutions. While solvents may be used as the medium for the dispersion or solution, water is preferred. Aqueous dispersions or aqueous solutions of urethane resins include forced emulsification types using emulsifiers, self-emulsifying types with hydrophilic groups introduced into the structure of the urethane resin, and water-soluble types. In particular, self-emulsifying types, which are ionomerized by introducing ionic groups into the structure of the urethane resin, are preferred due to their excellent storage stability, water resistance, and transparency of the resulting primer layer.

[0133] Various ionic groups can be introduced into the structure of the urethane resin, including carboxyl groups, sulfonic acid groups, phosphate groups, phosphonic acid groups, and quaternary ammonium bases, but carboxyl groups are preferred. It is preferable to neutralize the carboxyl groups with a neutralizing agent such as ammonia, amines, alkali metals, or inorganic alkalis to obtain a salt. Particularly preferred neutralizing agents are ammonia, trimethylamine, and triethylamine. In a urethane resin having carboxyl groups neutralized with a neutralizing agent, the carboxyl groups from which the neutralizing agent has been removed during the drying process after coating can be used as crosslinking reaction sites by a crosslinking agent. This results in excellent stability in the liquid state before coating, and further improves the durability, solvent resistance, water resistance, and blocking resistance of the resulting primer layer.

[0134] Various methods can be used to introduce carboxyl groups into urethane resins at each stage of the polymerization reaction. For example, one method is to use a resin containing carboxyl groups as a copolymer component during prepolymer synthesis, or to use a component containing carboxyl groups as one of the components of a polyol, polyisocyanate compound, or chain extender. In particular, a method using a carboxyl group-containing diol and introducing a desired amount of carboxyl groups by adjusting the amount of this component added is preferred. For example, a carboxyl group-containing diol can be copolymerized with a diol used in the synthesis of urethane resin. Examples of carboxyl group-containing diols include dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, bis-(2-hydroxyethyl)butanoic acid, and salts obtained by neutralizing their carboxyl groups with a neutralizing agent.

[0135] The primer layer preferably contains a compound derived from a crosslinking agent to strengthen the primer layer and improve performance such as adhesion. Known materials can be used as crosslinking agents, such as melamine compounds, oxazoline compounds, isocyanate compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds. Among these, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferred, and from the viewpoint of further improving adhesion and durability, melamine compounds, oxazoline compounds, isocyanate compounds, and epoxy compounds are more preferred, with melamine compounds, oxazoline compounds, and isocyanate compounds being particularly preferred. These crosslinking agents may be used individually or in combination of two or more. In some cases, using two or more in combination may further improve adhesion and durability.

[0136] Melamine compounds are compounds that have a melamine skeleton within them. Examples include alkylolated melamine derivatives, compounds obtained by reacting alkylolated melamine derivatives with alcohol to partially or completely etherify them, and mixtures thereof. Examples of alcohols used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, and isobutanol. Melamine compounds may be monomers or polymers of two or more forms, or mixtures thereof may be used. Furthermore, compounds in which urea or the like is co-condensed with a portion of the melamine can also be used, and catalysts can be used to increase the reactivity of the melamine compound. As for melamine compounds, those having a hydroxyl group are preferred considering their reactivity with various compounds.

[0137] Isocyanate compounds are compounds that have an isocyanate derivative structure, such as isocyanate compounds or blocked isocyanate compounds. Examples of isocyanate compounds include aromatic isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, methylenediphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; aliphatic isocyanate compounds having an aromatic ring such as α,α,α',α'-tetramethylxylylene diisocyanate; aliphatic isocyanate compounds such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic isocyanate compounds such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), and isopropylidene dicyclohexyl diisocyanate. Furthermore, polymers and derivatives of these isocyanate compounds, such as biuretized, isocyanurateized, uretdioneized, and carbodiimide-modified compounds, are also mentioned. These may be used individually or in combination of two or more. Among the above isocyanate compounds, aliphatic isocyanate compounds or alicyclic isocyanate compounds are more preferred than aromatic isocyanate compounds from the viewpoint of avoiding yellowing due to ultraviolet light.

[0138] Examples of blocked isocyanate compounds include those in which the isocyanate group of the above-mentioned isocyanate compounds is blocked by a blocking agent. Examples of blocking agents include phenolic compounds such as bisulfites, phenol, cresol, and ethylphenol; alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol; active methylene compounds such as dimethyl malonate, diethyl malonate, methyl isobutanoylacetate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; lactam compounds such as ε-caprolactam and δ-valerolactam; amine compounds such as diphenylaniline, aniline, and ethyleneimine; acid amide compounds such as acetanilide and acetic acid amide; and oxime compounds such as formaldehyde, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime. These may be used individually or in combination of two or more. As for the blocked isocyanate compound, isocyanate compounds blocked by an active methylene compound are preferred from the viewpoint of being less likely to damage the primer layer.

[0139] Isocyanate compounds may be used individually or as mixtures or binders with various polymers. It is preferable to use mixtures or binders with polyester resins or urethane resins to improve the dispersibility and crosslinking properties of isocyanate compounds.

[0140] Oxazoline compounds are compounds having an oxazoline group in their molecule. Polymers containing an oxazoline group are preferred as oxazoline compounds. Polymers containing an oxazoline group can be obtained by polymerization of an addition-polymerizable oxazoline group-containing monomer alone or with other monomers. Examples of addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. These may be used individually or in combination of two or more. Among these, 2-isopropenyl-2-oxazoline is preferred because it is readily available industrially. Other monomers are not particularly limited as long as they are copolymerizable with addition-polymerizable oxazoline group-containing monomers, and examples include (meth)acrylates such as alkyl (meth)acrylates; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid, and their sodium salts, potassium salts, ammonium salts, and tertiary amine salts; unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated amides such as (meth)acrylamide, N-alkyl(meth)acrylamide, and N,N-dialkyl(meth)acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; and α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene. Examples of alkyl groups in the alkyl (meth)acrylate, N-alkyl (meth)acrylamide, and N,N-dialkyl (meth)acrylamide include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, and cyclohexyl groups. These other monomers may be used individually or in combination of two or more.

[0141] The amount of oxazoline groups per gram of the oxazoline compound is preferably in the range of 0.5 to 10 mmol / g, more preferably 1 to 9 mmol / g, even more preferably 3 to 8 mmol / g, and particularly preferably 4 to 6 mmol / g. If the amount of oxazoline groups is within the above range, the durability of the coating film is improved and the adhesion can be easily adjusted.

[0142] Epoxy compounds are compounds that contain epoxy groups within their molecules. Examples of epoxy compounds include condensates of epichlorohydrin and compounds containing hydroxyl or amino groups. Examples of compounds containing hydroxyl or amino groups include ethylene glycol, polyethylene glycol, glycerin, polyglycerin, and bisphenol A. Examples of epoxy compounds include polyepoxy compounds, diepoxy compounds, monoepoxy compounds, and glycidylamine compounds.

[0143] Examples of polyepoxy compounds include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris(2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. Examples of diepoxy compounds include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether. Examples of monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. Examples of glycidylamine compounds include N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylamino)cyclohexane.

[0144] Carbodiimide compounds are compounds that have one or more carbodiimide structures or carbodiimide derivative structures in their molecule. Among carbodiimide compounds, polycarbodiimide compounds having two or more carbodiimide structures or carbodiimide derivative structures in their molecule are more preferable for better primer layer strength and other properties.

[0145] Carbodiimide compounds can be synthesized using known techniques, and generally, condensation reactions of diisocyanate compounds are employed. The diisocyanate compound is not particularly limited and can be either aromatic or aliphatic. Specifically, examples include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.

[0146] To improve the water solubility and water dispersibility of polycarbodiimide compounds, surfactants may be added, or hydrophilic monomers such as polyalkylene oxides, quaternary ammonium salts of dialkylamino alcohols, and hydroxyalkyl sulfonates may be added, to the extent that the effects of the present invention are not lost.

[0147] Silane coupling compounds are organosilicon compounds that contain both an organic functional group and a hydrolyzable group such as an alkoxy group within a single molecule. Examples of silane coupling compounds include epoxy group-containing compounds such as 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; styryl group-containing compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane; (meth)acryloyl group-containing compounds such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, and 3-(meth)acryloxypropylmethyldiethoxysilane; and N-2 Examples include amino group-containing compounds such as -(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane; isocyanurate group-containing compounds such as tris(trimethoxysilylpropyl)isocyanurate and tris(triethoxysilylpropyl)isocyanurate; and mercapto group-containing compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane.

[0148] Among the above compounds, epoxy group-containing silane coupling compounds, double bond-containing silane coupling compounds such as vinyl groups and (meth)acrylic groups, and amino group-containing silane coupling compounds are more preferred from the viewpoint of the strength of the primer layer.

[0149] The crosslinking agent reacts during the drying and film formation processes, improving the performance of the primer layer. It can be inferred that the formed primer layer contains compounds derived from the crosslinking agent, such as unreacted crosslinking agents, reacted compounds, or mixtures thereof.

[0150] The primer layer may contain particles for blocking or improving lubricity. The primer layer may also contain additives such as defoamers, coating modifiers, thickeners, organic lubricants, UV absorbers, antioxidants, foaming agents, dyes, and pigments, as needed, without impairing the spirit of the present invention.

[0151] The proportion of resin in 100% by mass of the primer layer is, for example, 5% by mass or more, preferably 5 to 99% by mass, more preferably 10 to 99% by mass, even more preferably 20 to 95% by mass, and particularly preferably 30 to 90% by mass. When the proportion of resin is within the above range, the adhesion performance and appearance of the primer layer are better.

[0152] The proportion of crosslinking agent-derived compounds in 100% by mass of the primer layer is, for example, 80% by mass or less, preferably 0.5 to 80% by mass, more preferably 0.5 to 65% by mass, even more preferably 3 to 50% by mass, and particularly preferably 5 to 40% by mass. When the proportion of crosslinking agent-derived compounds is within the above range, the adhesion performance and strength of the primer layer are better.

[0153] The thickness of the primer layer cannot be generalized as it depends on the material used for the primer layer and the performance to be achieved, but it is preferably in the range of 0.001 to 10 μm, more preferably 0.01 to 4 μm, and even more preferably 0.02 to 1 μm. The primer layer can be formed by known methods.

[0154] (Backside Functional Layer) A backside functional layer may be provided on the side of the transparent substrate opposite to the cured film side. The backside functional layer is a layer for providing various functions to the side of the transparent substrate opposite to the cured film side. Examples of backside functional layers include an adhesive layer, an antistatic layer, a refractive index adjusting layer, and an antiblocking layer. The backside functional layer may have multiple functions in a single layer, or it may be composed of multiple layers. An adhesive layer is provided to bond the film to various adherends. An antistatic layer is provided to prevent the adhesion of surrounding dust and other particles due to peeling charge or triboelectric charge to the outermost surface of the film, especially the outermost surface of the transparent substrate opposite to the cured film side, and the resulting defects. A refractive index adjusting layer is provided, for example, to improve the total light transmittance of the film. An antiblocking layer is provided to reduce blocking of the film.

[0155] As the adhesive for forming the adhesive layer, known adhesives can be used, including acrylic, polyester, urethane, and rubber-based adhesives. Among these, acrylic adhesives are preferred considering their versatility.

[0156] The thickness of the functional backing layer cannot be generalized as it depends on the material used for the functional backing layer and the performance to be achieved, but for example, it is 0.001 to 30 μm. If the functional backing layer is an adhesive layer, it is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. If the functional backing layer is an antistatic layer, it is preferably 0.001 to 10 μm, more preferably 0.01 to 5 μm.

[0157] The functional back layer can be formed by known methods. Preferably, the functional back layer is formed by coating a transparent substrate with a liquid prepared by adjusting the solid content concentration of the above-mentioned series of compounds as a solution or dispersion in a solvent to approximately 0.1 to 80% by mass. The functional back layer may also be formed after the cured film has been formed.

[0158] Conventional coating methods can be used to form the functional layer on the back surface, such as gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, kiss coating, spray coating, calender coating, and extrusion coating.

[0159] The drying and curing conditions for forming the functional layer on the back surface are not particularly limited, but in the case of a coating method, the drying temperature of the solvent such as water used in the coating liquid is usually in the range of 50 to 150°C, preferably 80 to 130°C, and more preferably 90 to 120°C. The drying time is approximately in the range of 3 to 200 seconds, preferably 5 to 120 seconds. In addition, in order to improve the strength of the functional layer on the back surface, if it is carried out in the film manufacturing process, a heat treatment step is usually performed in the range of 150 to 270°C, preferably 170 to 230°C, and more preferably 180 to 210°C. The time for this heat treatment step is approximately in the range of 3 to 200 seconds, preferably 5 to 120 seconds.

[0160] (Surface Functional Layer) The film may further have a surface functional layer on top of the cured film. Examples of surface functional layers include an antifouling layer, an antistatic layer, a refractive index adjusting layer (anti-reflective layer, low-reflection layer, etc.), an infrared absorption layer, an ultraviolet absorption layer, a color correction layer, etc. A single surface functional layer may have multiple functions, or it may be composed of multiple layers.

[0161] The antifouling layer is provided to improve the antifouling performance of the cured film by imparting water-repellent and oil-repellent properties. Conventional known materials such as silicone compounds, fluorine compounds, and long-chain alkyl group-containing compounds can be used for the antifouling layer. Among these, silicone compounds and fluorine compounds are preferred for exhibiting stronger antifouling performance, and fluorine compounds and long-chain alkyl group-containing compounds are preferred from the viewpoint of not contaminating the surface the antifouling layer comes into contact with.

[0162] Silicone compounds are compounds that have a silicone structure within their molecule. Examples include alkyl silicones such as dimethyl silicone and diethyl silicone, as well as phenyl silicones and methylphenyl silicones that have a phenyl group. Silicones with various functional groups can also be used, such as ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and various aromatic groups. Other common functional groups include silicones with vinyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms. It is also possible to use both in combination as addition-type silicones (types resulting from the addition reaction of vinyl groups and hydrogensilane). Furthermore, a method of introducing a double bond such as an acryloyl group and reacting at the double bond site is also preferred.

[0163] Furthermore, modified silicones such as acrylic grafted silicone, silicone grafted acrylic, amino-modified silicone, and perfluoroalkyl-modified silicone can also be used as silicone compounds. Considering heat resistance and stain resistance, it is preferable to use a curable silicone resin, and any type of curing reaction, such as condensation type, addition type, or active energy ray curing type, can be used.

[0164] Fluorine compounds are compounds that contain a fluorine atom. Organic fluorine compounds are preferably used as fluorine compounds, and examples include perfluoroalkyl group compounds, polymers of olefin compounds containing a fluorine atom, and aromatic fluorine compounds such as fluorobenzene. From the viewpoint of release properties, compounds containing a perfluoroalkyl group are preferred. Furthermore, fluorine compounds containing long-chain alkyl compounds, as described later, can also be used.

[0165] Examples of compounds containing perfluoroalkyl groups include perfluoroalkyl group-containing (meth)acrylates and their polymers, such as perfluoroalkyl (meth)acrylate, perfluoroalkyl methyl (meth)acrylate, 2-perfluoroalkyl ethyl (meth)acrylate, 3-perfluoroalkyl propyl (meth)acrylate, 3-perfluoroalkyl-1-methylpropyl (meth)acrylate, and 3-perfluoroalkyl-2-propenyl (meth)acrylate; and perfluoroalkyl group-containing vinyl ethers and their polymers, such as perfluoroalkyl methyl vinyl ether, 2-perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, and 3-perfluoroalkyl-2-propenyl vinyl ether. Considering heat resistance and stain resistance, compounds containing perfluoroalkyl groups are preferably polymers. The polymer may be a polymer of a single compound or a polymer of multiple compounds. Furthermore, from the viewpoint of stain resistance, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. It may also be a polymer with a compound containing a long-chain alkyl compound, as described later.

[0166] Long-chain alkyl group-containing compounds are compounds having a linear or branched alkyl group with typically 6 or more carbon atoms, preferably 8 or more, and more preferably 12 or more. Examples of alkyl groups include hexyl, octyl, decyl, lauryl, octadecyl, and behenyl groups. Examples of long-chain alkyl group-containing compounds include various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. Considering heat resistance and stain resistance, it is preferable that the long-chain alkyl group-containing compound is a polymer compound. Furthermore, from the viewpoint of effectively obtaining antifouling properties, it is even more preferable that the polymer compound has a long-chain alkyl group as a side chain.

[0167] Polymer compounds having long-chain alkyl groups as side chains can be obtained, for example, by reacting a polymer having a reactive group with a compound having an alkyl group that can react with the reactive group. Examples of the reactive group include hydroxyl groups, amino groups, carboxyl groups, and acid anhydride groups. Examples of polymers having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, reactive group-containing polyester resin, and reactive group-containing poly(meth)acrylic resin. Among these, polyvinyl alcohol is preferred considering its stain resistance and ease of handling.

[0168] Examples of compounds having alkyl groups that can react with the above-mentioned reactive groups include long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate; long-chain alkyl group-containing acid chlorides such as hexyl chloride, octyl chloride, decyl chloride, lauryl chloride, octadecyl chloride, and behenyl chloride; long-chain alkyl group-containing amines; and long-chain alkyl group-containing alcohols. Among these, long-chain alkyl group-containing isocyanates are preferred considering their release properties and ease of handling, and octadecyl isocyanate is particularly preferred.

[0169] Polymeric compounds having long-chain alkyl groups as side chains can also be obtained by polymerization of long-chain alkyl (meth)acrylates or by copolymerization of long-chain alkyl (meth)acrylates with other vinyl group-containing monomers. Examples of long-chain alkyl (meth)acrylates include hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate.

[0170] The amount of antifouling material in the surface functional layer that exhibits the above-mentioned antifouling performance cannot be stated definitively as it depends on the material used, but in the case of silicone compounds and fluorine compounds, it is usually in the range of 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, and the upper limit may be 100% by mass. In the case of long-chain alkyl group-containing compounds, it is usually in the range of 0.1% by mass or more, preferably 1% by mass or more, and even more preferably 3% by mass or more, and the upper limit may be 100% by mass. Effective antifouling performance can be achieved by using the above ranges.

[0171] When forming an antistatic layer as a surface functional layer, various conventionally known antistatic agents can be used. Alternatively, a method is also preferred in which a double bond, such as an acryloyl group, is introduced into a compound having an ammonium group, and the reaction occurs at the double bond.

[0172] Examples of refractive index adjusting layers include high refractive index layers, low refractive index layers, and laminates thereof. When forming a refractive index adjusting layer as a surface functional layer, if the goal is to increase the refractive index, examples of materials used include aromatic compounds such as benzene structures, bisphenol A structures, melamine structures, and fluorene structures; condensed polycyclic aromatic compounds such as naphthalene, anthracene, phenanthrene, naphthalene, benzo[a]anthracene, benzo[a]phenanthrene, pyrene, benzo[c]phenanthrene, and perylene structures, which are considered to be high refractive index compounds among aromatics; metal oxides such as zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimony oxide, yttrium oxide, indium oxide, cerium oxide, ATO (antimony-tin oxide), ITO (indium-tin oxide); metal chelate compounds such as titanium chelate and zirconium chelate; compounds containing sulfur elements; and compounds containing halogen elements.

[0173] Because metal oxides may have reduced adhesion depending on the application, it is preferable to use them in granular form. Furthermore, from the viewpoint of the appearance of the coating, the average particle size is preferably in the range of 100 nm or less, more preferably 50 nm or less, and even more preferably 25 nm or less.

[0174] When forming a refractive index adjustment layer as a surface functional layer, if the goal is to lower the refractive index, conventionally known materials can be used. For example, acrylic resins and urethane resins are generally suitable because they have low refractive indices. In particular, compounds in which fluorine atoms are incorporated into the resin, such as fluororesins, compounds containing fluororesin in the main skeleton, and compounds containing perfluoroalkyl groups in the side chains, are also suitable. Inorganic materials include, for example, hollow silica particles, fluorine-containing inorganic compounds such as magnesium fluoride and calcium fluoride, and their hollow or nanoporous particles.

[0175] The thickness of the surface functional layer is preferably five times or less the height from the recess to the protrusion of the uneven structure of the cured film. This is because if the thickness exceeds five times the height of the unevenness, the matte finish due to the unevenness will be reduced. The thickness of the surface functional layer cannot be generalized as it depends on the height of the unevenness, but it is usually in the range of 0.001 to 3 μm, preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm, even more preferably 0.02 to 0.5 μm, and particularly preferably 0.03 to 0.2 μm. By using the above range, it is possible to achieve both the expression of functionality by the surface functional layer and the matte finish due to the unevenness of the cured film. The surface functional layer can be formed by known methods.

[0176] The surface functional layer is preferably formed by coating the cured film with a liquid prepared by adjusting the solid content concentration of the above-mentioned series of compounds as a solution or dispersion in a solvent to approximately 0.1 to 80% by mass.

[0177] Conventional coating methods can be used to form the surface functional layer, such as gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, kiss coating, spray coating, calender coating, and extrusion coating.

[0178] The drying and curing conditions when forming the surface functional layer are not particularly limited. For example, in the case of coating, the drying of the solvent such as water used in the coating liquid is usually in the range of 50 to 150°C, preferably 80 to 130°C, and more preferably 90 to 120°C. The drying time is approximately in the range of 3 to 200 seconds, preferably 5 to 120 seconds. In addition, in order to improve the strength of the surface functional layer, if it is carried out in the film manufacturing process, a heat treatment process is usually performed in the range of 150 to 270°C, preferably 170 to 230°C, and more preferably 180 to 210°C. The time for this heat treatment process is approximately in the range of 3 to 200 seconds, preferably 5 to 120 seconds.

[0179] (Performance) The film according to the first embodiment described above can suppress reflections and glare from fluorescent lights, etc., and keep the haze below 60%, allowing for clear visibility of the display screen, while also having good scratch resistance, which is a weakness of matte laminated films. Thus, both anti-glare and scratch resistance can be achieved. Furthermore, the haze of the film can be reduced to below 60%. In particular, surface roughness Ra, length Rsm, inclination angle θα, Safc, maximum distance of unevenness Sz, root mean square gradient Sdq, and unfolded interface area ratio Sdr tend to correlate well with good scratch resistance and the achievement of desired matte and glossy properties. In high-definition display devices with fine pixel sizes, conventional surface unevenness sizes lead to a decrease in image quality, such as screen glare and blurred text. For example, in the case of high-definition display devices, conventional surface unevenness sizes are order of magnitude close to the pixel size of high-definition displays, and glare occurs due to the lens effect caused by surface unevenness. The cured film of the present invention is thought to reduce glare because the shape of the surface irregularities is controlled so as not to be spherical as in conventional films.

[0180] 2. Second Embodiment The cured film of the film according to the second embodiment is a cured product of a curable composition. The irregular wrinkle-like uneven structure formed on the surface of the cured film in the second embodiment has a root mean square gradient Sdq of the coating surface defined by ISO 25178 of less than 0.3, an unfolded interface area ratio Sdr of the coating surface defined by ISO 25178 of 3.0% or less, and a maximum distance Sz from the highest point to the lowest point of the uneven surface defined by ISO 25178 of 6.0 μm or less. In addition, the haze of the film according to the second embodiment is 60% or less.

[0181] In the second embodiment, the root mean square gradient Sdq of the coating surface with an irregular wrinkle-like uneven structure, as defined in ISO 25178, is less than 0.30, preferably 0.25 or less, more preferably 0.20 or less, and may be 0.01 or more, 0.05 or more, or 0.10 or more, for the same reasons as in the first embodiment. The lower and upper limits of the root mean square gradient Sdq can be arbitrarily combined, for example, 0.01 or more and less than 0.30, 0.05 to 0.25, or 0.10 to 0.20.

[0182] In the second embodiment, the unfolded interface area ratio Sdr of the coating surface defined in ISO 25178 for the irregular wrinkle-like uneven structure is 3.0% or less, preferably 2.5% or less, more preferably 2.0% or less, and may also be 0.1% or more, 0.3% or more, or 0.5% or more, for the same reasons as in the first embodiment. The lower and upper limits of the unfolded interface area ratio Sdr can be arbitrarily combined, for example, 0.1 to 3.0%, 0.3 to 2.5%, or 0.5 to 2.0%.

[0183] The haze of the film according to the second embodiment is 60% or less, preferably 55% or less, more preferably 50% or less, and may also be 4.0% or more, 6.0% or more, or 8.0% or more, for the same reasons as in the first embodiment. The lower and upper limits of the haze of the film can be arbitrarily combined, for example, 4.0 to 60%, 6.0 to 55%, or 8.0 to 50%.

[0184] In the second embodiment, the arithmetic mean roughness Ra of the roughness curve element of the irregular wrinkle-like uneven structure according to JIS B0601:2013 is preferably 1.0 μm or less, more preferably 0.8 μm or less, even more preferably 0.7 μm or less, and may also be 0.1 μm or more, 0.2 μm or more, or 0.3 μm or more, for the same reasons as in the first embodiment. The lower and upper limits of the mean roughness Ra can be arbitrarily combined, for example, 0.1 to 1.0 μm, 0.2 to 0.8 μm, or 0.3 to 0.7 μm.

[0185] In the second embodiment, the average length Rsm of the roughness curve elements of the irregular wrinkle-like uneven structure according to JIS B0601:2013 is preferably 30 μm or more, more preferably 33 μm or more, even more preferably 37 μm or more, and may also be 200 μm or less, 150 μm or less, or 100 μm or less, for the same reasons as in the first embodiment. The lower and upper limits of the average length Rsm can be arbitrarily combined, for example, 30 to 200 μm, 33 to 150 μm, or 37 to 100 μm.

[0186] In the second embodiment, the inclination angle θα of the roughness curve element of the irregular wrinkle-like uneven structure according to JIS B0601:2013 is preferably 6.0° or less, more preferably 5.5° or less, even more preferably 5.0° or less, and may also be 1.0° or more, 1.5° or more, or 2.0° or more, for the same reasons as in the first embodiment. The lower and upper limits of the inclination angle θα can be arbitrarily combined, for example, 1.0 to 6.0°, 1.5 to 5.5°, or 2.0 to 5.0°.

[0187] In the second embodiment, the 60° gloss of the surface of the cured film is preferably 10 or more, more preferably 15 or more, even more preferably 20 or more, and may also be 50 or less, 45 or less, or 40 or less, for the same reasons as in the first embodiment. The lower and upper limits of the 60° gloss of the surface of the cured film can be arbitrarily combined, for example, 10 to 50, 15 to 45, or 20 to 40.

[0188] In the second embodiment, the 20° gloss of the surface of the cured film is preferably 3.0 or higher, more preferably 5.0 or higher, even more preferably 6.0 or higher, and may also be 30 or lower, 25 or lower, or 20 or lower, for the same reasons as in the first embodiment. The lower and upper limits of the 20° gloss of the surface of the cured film can be arbitrarily combined, for example, 3.0 to 30, 5.0 to 25, or 6.0 to 20.

[0189] In the second embodiment, the Scale area fractal complexity (Safc) of the irregular wrinkled uneven structure as defined in ISO 25178 is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and may also be 0.1 or more, 0.5 or more, or 1.0 or more, for the same reasons as in the first embodiment. The lower and upper limits of Safc can be arbitrarily combined, for example, 0.1 to 5.0, 0.5 to 4.0, or 1.0 to 3.0.

[0190] In the second embodiment, the maximum distance Sz from the highest point to the lowest point of the uneven surface defined in ISO 25178 for the irregular wrinkle-like uneven structure is preferably 6.0 μm or less, more preferably 5.5 μm or less, even more preferably 5.0 μm or less, and may also be 0.1 μm or more, 1.0 μm or more, or 2.0 μm or more, for the same reasons as in the first embodiment. The lower and upper limits of the maximum distance Sz can be arbitrarily combined, for example, 0.1 to 6.0 μm, 1.0 to 5.5 μm, or 2.0 to 5.0 μm.

[0191] The curable composition used in the second embodiment preferably contains at least one polyfunctional (meth)acrylate having two or more polymerizable double bonds, for example, two or more (meth)acryloyl groups, in one molecule; more preferably contains at least one difunctional (meth)acrylate and one trifunctional or more functional (meth)acrylate; and even more preferably contains at least one difunctional (meth)acrylate, one tri- to hexafunctional (meth)acrylate, and one heptafunctional or more functional (meth)acrylate. The difunctional (meth)acrylate, one trifunctional or more functional (meth)acrylate, one tri- to hexafunctional (meth)acrylate, and one heptafunctional or more functional (meth)acrylate are as described in the first embodiment, and the preferred embodiment is the same.

[0192] The curable composition used in the second embodiment may contain one or more selected from urethane (meth)acrylate, acrylic (meth)acrylate, and monofunctional (meth)acrylate. Furthermore, the curable composition used in the second embodiment may also contain curable compounds other than (meth)acrylate that can be cured by vacuum ultraviolet irradiation. The curable compounds other than urethane (meth)acrylate, acrylic (meth)acrylate, monofunctional (meth)acrylate, and (meth)acrylate that can be cured by vacuum ultraviolet irradiation are as described in the first embodiment, and the preferred embodiment is similar.

[0193] The curable composition used in the second embodiment may further contain one or more selected from particles, a photopolymerization initiator, and an organic solvent. The particles, photopolymerization initiator, and organic solvent are as described in the first embodiment, and the preferred embodiment is the same.

[0194] The composition of the curable composition in the second embodiment is not particularly limited, but for example, a composition similar to that in the first embodiment can be adopted, and the same applies to the preferred embodiment.

[0195] The description of the transparent substrate, the method for manufacturing the film, the primer layer, the back functional layer, and the front functional layer in the first embodiment can also be applied to the second embodiment.

[0196] (Performance) The film according to the second embodiment described above can suppress reflections and glare from fluorescent lights, etc., and keep the haze below 60%, allowing for clear visibility of the display screen, while also having good scratch resistance, which is a weakness of matte laminated films. Thus, both anti-glare properties and scratch resistance can be achieved. Furthermore, the haze of the film can be reduced to below 60%. In particular, surface roughness Ra, length Rsm, inclination angle θα, Safc, maximum distance of irregularities Sz, root mean square gradient Sdq, and unfolded interface area ratio Sdr tend to correlate well with good scratch resistance and the achievement of desired matte and glossy properties.

[0197] 3. Third Embodiment The film according to the third embodiment comprises a transparent substrate and a cured film provided on the surface of the transparent substrate, wherein the cured film is a cured product of a curable composition. The curable composition of the film according to the third embodiment contains a difunctional (meth)acrylate, a trifunctional to hexafunctional (meth)acrylate, and a heptafunctional or higher (meth)acrylate, wherein the proportion of the heptafunctional or higher (meth)acrylate is 50% by mass or more of the total mass of nonvolatile matter of the curable composition. The difunctional (meth)acrylate, trifunctional to hexafunctional (meth)acrylate, and heptafunctional or higher (meth)acrylate are as described in the first embodiment, and the preferred embodiment is similar.

[0198] The composition of the curable composition used in the third embodiment is not particularly limited, as long as the proportion of heptafunctional (meth)acrylate is 50% by mass or more relative to the total mass of nonvolatile components of the curable composition.

[0199] The proportion of heptafunctional or more (meth)acrylate in the curable composition used in the third embodiment is preferably 50 to 94.9% by mass, more preferably 55 to 91% by mass, and even more preferably 60 to 80% by mass, of the total mass of nonvolatile components of the curable composition. When the proportion of heptafunctional or more (meth)acrylate is above the lower limit of the above numerical range, a film with improved scratch resistance and durability is easily obtained. When the proportion of heptafunctional or more (meth)acrylate is below the upper limit of the above numerical range, a film with good quality unevenness can be formed, and a film with the desired matte finish is easily obtained. At the same time, a film with excellent curlability and processability is easily obtained.

[0200] The proportion of 3- to 6-functional (meth)acrylates in the curable composition used in the third embodiment is preferably 5 to 49.5% by mass, more preferably 8 to 44% by mass, and even more preferably 10 to 30% by mass, based on the total mass of nonvolatile components of the curable composition. When the proportion of 3- to 6-functional (meth)acrylates is above the lower limit of the above numerical range, a film with improved scratch resistance and durability is easily obtained. When the proportion of 3- to 6-functional (meth)acrylates is below the upper limit of the above numerical range, a film with good quality unevenness can be formed, and a film with improved matte finish is easily obtained. At the same time, a film with excellent curlability and processability is easily obtained.

[0201] The proportion of difunctional (meth)acrylate in the curable composition used in the third embodiment is preferably 0.1 to 45% by mass, more preferably 1 to 35% by mass, and even more preferably 10 to 20% by mass, based on the total mass of nonvolatile components of the curable composition. When the proportion of difunctional (meth)acrylate is above the lower limit of the above numerical range, a film with excellent workability due to low viscosity and suppression of curl due to curing shrinkage is easily obtained. When the proportion of difunctional (meth)acrylate is below the upper limit of the above numerical range, a film with excellent scratch resistance and durability is easily obtained.

[0202] The curable composition used in the third embodiment may contain one or more selected from urethane (meth)acrylate, acrylic (meth)acrylate, and monofunctional (meth)acrylate. Furthermore, the curable composition used in the third embodiment may also contain curable compounds other than (meth)acrylate that can be cured by vacuum ultraviolet irradiation. The curable compounds other than urethane (meth)acrylate, acrylic (meth)acrylate, monofunctional (meth)acrylate, and (meth)acrylate that can be cured by vacuum ultraviolet irradiation are as described in the first embodiment, and the preferred embodiment is similar.

[0203] The curable composition used in the third embodiment may further contain one or more selected from particles, a photopolymerization initiator, and an organic solvent. The particles, photopolymerization initiator, and organic solvent are as described in the first embodiment, and the same applies to the preferred embodiment.

[0204] In the third embodiment, the proportion of components other than difunctional (meth)acrylates, triplicate to heptatic (meth)acrylates, and heptatic or more (meth)acrylates in the curable composition is not particularly limited and can be the same as, for example, the proportion of those components in the first embodiment, and the same applies to the preferred embodiment.

[0205] In the third embodiment, the root mean square gradient Sdq of the coating surface with an irregular wrinkle-like uneven structure as defined in ISO 25178 is preferably less than 0.30, more preferably 0.25 or less, even more preferably 0.20 or less, and may also be 0.01 or more, 0.05 or more, or 0.10 or more, for the same reasons as in the first embodiment. The lower and upper limits of the root mean square gradient Sdq can be arbitrarily combined, for example, 0.01 or more and less than 0.30, 0.05 to 0.25, or 0.10 to 0.20.

[0206] In the third embodiment, the unfolded interface area ratio Sdr of the coating surface defined in ISO 25178 for the irregular wrinkle-like uneven structure is preferably 3.0% or less, more preferably 2.5% or less, even more preferably 2.0% or less, and may also be 0.1% or more, 0.3% or more, or 0.5% or more, for the same reasons as in the first embodiment. The lower and upper limits of the unfolded interface area ratio Sdr can be arbitrarily combined, for example, 0.1 to 3.0%, 0.3 to 2.5%, or 0.5 to 2.0%.

[0207] The haze of the film according to the third embodiment is preferably 60% or less, more preferably 55% or less, even more preferably 50% or less, and may be 4.0% or more, 6.0% or more, or 8.0% or more, for the same reasons as in the first embodiment. The lower and upper limits of the haze of the film can be arbitrarily combined, for example, 4.0 to 60%, 6.0 to 55%, or 8.0 to 50%.

[0208] In the third embodiment, the arithmetic mean roughness Ra of the roughness curve element of the irregular wrinkle-like uneven structure according to JIS B0601:2013 is preferably 1.0 μm or less, more preferably 0.8 μm or less, even more preferably 0.7 μm or less, and may also be 0.1 μm or more, 0.2 μm or more, or 0.3 μm or more, for the same reasons as in the first embodiment. The lower and upper limits of the mean roughness Ra can be arbitrarily combined, for example, 0.1 to 1.0 μm, 0.2 to 0.8 μm, or 0.3 to 0.7 μm.

[0209] In the third embodiment, the average length Rsm of the roughness curve elements of the irregular wrinkle-like uneven structure according to JIS B0601:2013 is preferably 30 μm or more, preferably 33 μm or more, more preferably 37 μm or more, and may also be 200 μm or less, 150 μm or less, or 100 μm or less, for the same reasons as in the first embodiment. The lower and upper limits of the average length Rsm can be arbitrarily combined, for example, 30 to 200 μm, 33 to 150 μm, or 37 to 100 μm.

[0210] In the third embodiment, the inclination angle θα of the roughness curve element of the irregular wrinkle-like uneven structure according to JIS B0601:2013 is preferably 6.0° or less, more preferably 5.5° or less, even more preferably 5.0° or less, and may also be 1.0° or more, 1.5° or more, or 2.0° or more, for the same reasons as in the first embodiment. The lower and upper limits of the inclination angle θα can be arbitrarily combined, for example, 1.0 to 6.0°, 1.5 to 5.5°, or 2.0 to 5.0°.

[0211] In the third embodiment, the 60° gloss of the surface of the cured film is preferably 10 or more, more preferably 15 or more, even more preferably 20 or more, and may also be 50 or less, 45 or less, or 40 or less, for the same reasons as in the first embodiment. The lower and upper limits of the 60° gloss of the surface of the cured film can be arbitrarily combined, for example, 10 to 50, 15 to 45, or 20 to 40.

[0212] In the third embodiment, the 20° gloss of the surface of the cured film is preferably 3.0 or higher, more preferably 5.0 or higher, even more preferably 6.0 or higher, and may also be 30 or lower, 25 or lower, or 20 or lower, for the same reasons as in the first embodiment. The lower and upper limits of the 20° gloss of the surface of the cured film can be arbitrarily combined, for example, 3.0 to 30, 5.0 to 25, or 6.0 to 20.

[0213] In the third embodiment, the Scale area fractal complexity (Safc) of the irregular wrinkled uneven structure as defined in ISO 25178 is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and may also be 0.1 or more, 0.5 or more, or 1.0 or more, for the same reasons as in the first embodiment. The lower and upper limits of Safc can be arbitrarily combined, for example, 0.1 to 5.0, 0.5 to 4.0, or 1.0 to 3.0.

[0214] In the third embodiment, the maximum distance Sz from the highest point to the lowest point of the uneven surface defined in ISO 25178 for the irregular wrinkle-like uneven structure is preferably 6.0 μm or less, more preferably 5.5 μm or less, even more preferably 5.0 μm or less, and may also be 0.1 μm or more, 1.0 μm or more, or 2.0 μm or more, for the same reasons as in the first embodiment. The lower and upper limits of the maximum distance Sz can be arbitrarily combined, for example, 0.1 to 6.0 μm, 1.0 to 5.5 μm, or 2.0 to 5.0 μm.

[0215] The method for manufacturing a film according to the third embodiment can be carried out in the same manner as in the first embodiment, except that a curable composition is used that contains a difunctional (meth)acrylate, a trifunctional to hexafunctional (meth)acrylate, and a heptafunctional or higher (meth)acrylate, wherein the proportion of the heptafunctional or higher (meth)acrylate is 50% by mass or more of the total mass of nonvolatile matter. The description of the transparent substrate, primer layer, back functional layer, and front functional layer in the first embodiment can also be applied to the third embodiment.

[0216] (Performance) The film according to the third embodiment described above can suppress reflections and glare from fluorescent lights, etc., and also has good scratch resistance, which is a weakness of matte laminated films, thus achieving both anti-glare properties and scratch resistance.

[0217] [Applications] The film of the present invention can be used, for example, as an anti-glare film. The film of the present invention is useful as a protective member for optical equipment such as cameras and other photographic devices and image display devices. Cameras and other photographic devices and image display devices are placed on the transparent substrate side of the film.

[0218] For example, the film of the present invention can be applied to the protective member of a camera module comprising a camera and a protective member. In the said camera module, the camera is located on the transparent substrate side. In addition, the film of the present invention can be applied to the protective member of an image display module comprising an image display device and a protective member. In the said image display module, the image display device is located on the transparent substrate side. The film of the present invention can also be suitably used in liquid crystal displays, in which case the liquid crystal display may be located on the transparent substrate side of the film. Furthermore, the film of the present invention is also useful when applied to polarizing plates, in which case the polarizing plate may be located on the transparent substrate side of the film.

[0219] The embodiments will be described in more detail below with reference to experimental examples, but the present invention is not limited to the following description.

[0220] The materials used in the experimental example are as follows: • PET film (thickness: 100 μm) • (Meth)acrylate (A): 1,6-hexanediol diacrylate (bifunctional acrylate) • (Meth)acrylate (B): Mixture of pentaerythritol triacrylate and pentaerythritol hexaacrylate (trifunctional acrylate, tetrafunctional acrylate) • (Meth)acrylate (C): Dipentaerythritol hexaacrylate (hexafunctional acrylate) • (Meth)acrylate (D): Urethane acrylate (Mitsubishi Chemical Corporation's Shiko UV-3200B) (bifunctional acrylate) • (Meth)acrylate (E): Urethane acrylate (Nemoto Kogyo Co., Ltd.'s Art Resin UN-904) (decafunctional acrylate) • (Meth)acrylate (F): Urethane acrylate (Mitsubishi Chemical Corporation's Shiko UT-5670) (hexafunctional or higher acrylate) • (Meth)acrylate (G): Acrylic acrylate with 7 or more functions as described below • (Meth)acrylate (H): Dicyclopentenyloxyethyl acrylate (monofunctional acrylate) • Particles (I): Aluminum oxide particle dispersion (ALMIBK30WT%-H06, manufactured by CIK Nanotech, average particle size 0.012 μm) • Particles (J): Crosslinked acrylic particles (MX-180TA, manufactured by Soken Chemical Co., Ltd., average particle size 1.8 μm) • Particles (K): PTFE-modified polyethylene wax (CERAFLOUR 998, manufactured by BIC Chemie Japan, average particle size 5 μm) • Photopolymerization initiator (L): Omnirad 184, manufactured by IGM Resins B.V.

[0221] (Meth)acrylate (G): As (meth)acrylate (G), specific hepta-functional or higher acrylic acrylates were prepared as follows. First, in a flask equipped with a thermometer, stirrer and reflux condenser, propylene glycol monomethyl ether (157 parts by mass), glycidyl methacrylate (98 parts by mass), methyl methacrylate (1.0 part by mass), ethyl acrylate (1.0 part by mass), mercaptopropyltrimethoxysilane (1.9 parts by mass), and 2,2'-azobis(2,4-dimethylvaleronitrile) (1.0 part by mass) were added and reacted at 65°C for 3 hours. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.5 parts by mass) was added and reacted for another 3 hours, after which propylene glycol monomethyl ether (138 parts by mass) and p-methoxyphenol (0.45 parts by mass) were added and heated to 100°C. Next, acrylic acid (51 parts by mass) and triphenylphosphine (3.1 parts by mass) were added and the mixture was reacted at 110°C for 6 hours. This yielded acrylic acrylate (G) as (meth)acrylate, which has a double bond in its side chain that is capable of radical polymerization. The double bond group concentration of the obtained acrylic acrylate, i.e., the acryloyl equivalent (amount of acryloyl group introduced), was 4.6 mmol / g, and the weight-average molecular weight (Mw) was 17,700.

[0222] [Measurement of Weight-Average Molecular Weight (Mw)] The weight-average molecular weight (Mw) of acrylic acrylate was measured using gel permeation chromatography (GPC) under the following conditions and determined as a converted value using polystyrene standards. "HLC-8120" (Tosoh Corporation) was used as the GPC, and TSKgel G5000HXL*GMHXL-L (Tosoh Corporation) was used as the column. Calibration curves were prepared using F288 / F80 / F40 / F10 / F4 / F1 / A5000 / A1000 / A500 (Tosoh Corporation) and styrene as standard polystyrenes. The measurement was performed using 100 μL of a solution in which acrylic acrylate was dissolved in tetrahydrofuran to a concentration of 0.4%, at a column oven temperature of 40°C.

[0223] [Raw materials for base materials] ・Polyester (S1): A polyethylene terephthalate homopolymer with an intrinsic viscosity of 0.63 dl / g, obtained using magnesium acetate tetrahydrate and tetrabutyl titanate as polymerization catalysts. ・Polyester (S2): A polyethylene terephthalate homopolymer with an intrinsic viscosity of 0.64 dl / g, obtained using magnesium acetate tetrahydrate, orthophosphoric acid, and germanium dioxide as polymerization catalysts. ・Polyester (S3): A polyethylene terephthalate homopolymer containing 0.3% by mass of silica particles with an average primary particle diameter of 2 μm.

[0224] [Composition for forming a primer layer] A composition for forming a primer layer was obtained by mixing the following polyester resin (P1), urethane resin (P2), melamine compound (P3), and particles (P4) in a ratio of polyester resin (P1) / urethane resin (P2) / melamine compound (P3) / particles (P4) (solid content mass ratio) = 60 / 25 / 10 / 5. • Polyester resin (P1): Aqueous dispersion of polyester resin with the following composition: monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfisoisophthalic acid / / (diol component) ethylene glycol / 1,4-butanediol / diethylene glycol = 56 / 40 / 4 / / 70 / 20 / 10 (mol%) • Urethane resin (P2): Aqueous dispersion of polyester-based urethane resin with the following composition: isophorone diisocyanate: terephthalic acid: isophthalic acid: ethylene glycol: diethylene glycol: dimethylolpropanoic acid = 12:19:18:21:25:5 (mol%) • Melamine compound (P3): Hexamethoxymethylolmelamine • Particles: (P4): Silica particles with an average primary particle diameter of 0.07 μm

[0225] [Transparent Substrate and Primer Layer] A raw material prepared by mixing polyester (S1), (S2), and (S3) in proportions of 91% by mass, 3% by mass, and 6% by mass, respectively, was used as the raw material for the outermost layer (surface layer), and a raw material prepared by mixing polyester (S1) and (S2) in proportions of 97% by mass and 3% by mass, respectively, was used as the raw material for the intermediate layer. These materials were supplied to two extruders, each melted at 285°C, and then co-extruded and cooled on a cooling roll set at 40°C in a layer configuration of two types and three layers (surface layer / intermediate layer / surface layer = 1:8:1 discharge volume) to obtain an unstretched sheet. Next, using the difference in roll peripheral speed, the film was stretched 3.1 times in the longitudinal direction at a film temperature of 85°C. A primer layer forming composition was applied to one side of this longitudinally stretched film, guided into a tenter, and dried at 95°C for 10 seconds. Next, the film was stretched 4.2 times in the transverse direction at 120°C, heat-treated at 230°C for 10 seconds, then relaxed by 2% in the transverse direction to obtain a polyester film substrate (transparent substrate) with a thickness (after drying) of 50 μm and a primer layer of 0.1 μm thickness on one side.

[0226] [Experimental Examples 1-11, 13, 14] (Meth)acrylate (A), (meth)acrylate (B), (meth)acrylate (C), (meth)acrylate (D), (meth)acrylate (E), (meth)acrylate (F), (meth)acrylate (G), (meth)acrylate (H), particles (I), particles (J), particles (K), and photopolymerization initiator (L) were mixed in the amounts (parts by mass, calculated on a non-volatile content basis) shown in Table 1. Methyl ethyl ketone was then added to achieve a solid content concentration of 40% by mass, and the mixture was stirred until homogeneous to obtain a curable composition. The curable composition was applied to a primer layer formed on the transparent substrate described above and dried at 70°C for 1 minute. Then, excimer light (half-width 14 nm) from xenon (wavelength 172 nm) was irradiated at a dose of 20 mJ / cm². ２ , illuminance 11mW / cm ２ The dried coating was irradiated with a Ushio Inc. xenon excimer 172nm light irradiation unit SVS3, lamp unit model: UEM343W-172ST (lamp house model: H2112, lighting power supply model: B0314), nitrogen flow (oxygen concentration 0.01% or less). Furthermore, the coating was irradiated with a high-pressure mercury lamp in an air atmosphere with an integrated light intensity of 300 mJ / cm². ２ , illuminance 150mW / cm ２A film was obtained on a PET film having a cured film on which ultraviolet light was irradiated using a UV conveyor (model: US5-X1802-X1202) manufactured by iGraphics Co., Ltd., with a thickness (after curing) of 5 μm and an uneven surface structure.

[0227] [Experimental Example 12] A film was obtained under the same conditions as in Experimental Examples 1 to 11, except that the composition of the curable composition was changed as shown in Table 1 and no excimer light irradiation was performed.

[0228]

[0229] [Measurement Method] (Ra, Rsm, θα, Safc, Sz, Sdq, Sdr) Using a surface topography system (Hitachi High-Tech Science Corporation's "Scanning White Air Interferometry Microscope VS1330"), the surface topography of a 703.12 μm × 937.42 μm area on the surface of the hardened film was measured by optical interferometry. The data was read after interpolation and baseline correction. The objective lens magnification during measurement was set to 20x.

[0230] (Total light transmittance, haze) The measurement target was a film in which a cured film was formed on a transparent substrate (PET film). Total light transmittance and haze were measured using a haze meter "SH7000" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z8722Z (Geometric conditions for irradiation and reception of light-transmitting objects), JIS K7361-1 (Plastics - Test method for total light transmittance of transparent materials), and JIS K7136 (Plastics - Method for determining haze of transparent materials).

[0231] (20° gloss, 60° gloss) Films with a cured film formed on a transparent substrate (PET film) were used as the measurement target. 20° gloss and 60° gloss (20° specular gloss, 60° specular gloss) were measured in accordance with JIS Z 8741 using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. A lower gloss value indicates better matte finish.

[0232] (Scratch Resistance Test) In accordance with JIS K7136:2000, the hardened film of the experimental example was subjected to a 1 kgf load applied to the steel wool using #0000 grade steel wool. The haze and gloss after 100 back-and-forth rubs of the hardened film surface were compared with the haze and gloss before rubbing. The change in each (absolute value) was judged according to the following criteria: ・Total light transmittance A: less than 1.0%, B: 1.0% or more and less than 3.0%, C: 3.0% or more. ・Haze A: less than 2.0%, B: 2.0% or more and less than 5.0%, C: 5.0% or more. ・20° gloss A: less than 1.0%, B: 1.0% or more and less than 3.0%, C: 3.0% or more. 60° Gross: A: Less than 3.0%, B: 3.0% or more but less than 5.0%, C: 5.0% or more.

[0233] (Glare) The film obtained in the experimental example was placed on a liquid crystal display of approximately 123 dpi (10.4 inches diagonally, XGA (1,024 x 768 dots)) and the presence or absence of glare was visually checked. A: No glare was observed at all. B: Glare was observed, but at a level that did not affect the deterioration of image quality. C: Glare was observed, and the image quality deteriorated slightly. D: Image quality was greatly impaired due to glare.

[0234] The results are shown in Table 2.

[0235]

[0236] In Experimental Examples 1-6, a single layer of the cured film exhibited excellent transparency, excellent anti-glare properties, and excellent scratch resistance. In contrast, the films in Experimental Examples 7-11 and Experimental Examples 13 and 14 had insufficient transparency, with haze exceeding 50%, raising concerns about reduced visibility.

[0237] In Experimental Example 12, the film was not irradiated with excimer light, so an irregular wrinkle-like uneven structure was not formed. Although anti-glare properties were obtained by incorporating a large amount of particles, the coating was scratched in the scratch resistance test, and it was not possible to maintain the same level of haze as before the test. In addition, the introduction of a large amount of particles also worsened glare.

[0238] Although the present invention has been described above with reference to specific embodiments, each embodiment is presented as an example and does not limit the scope of the present invention. Each embodiment described herein can be modified in various ways within the scope in which the effects of the invention are achieved, and can be combined with features described in other embodiments to the extent that is feasible.

[0239] According to the present invention, a film is provided that exhibits excellent transparency and excellent anti-glare properties, as well as excellent scratch resistance, even with only one layer of cured film; a method for manufacturing the film; a polarizing plate equipped with the film; a liquid crystal display; and an image display device.

[0240] 1. Film 2. Transparent substrate 3. Cured film

Claims

1. A film comprising a transparent substrate and a cured film provided on the surface of the transparent substrate, wherein the cured film is a cured product of a curable composition, the curable composition contains at least a difunctional (meth)acrylate and a trifunctional or more (meth)acrylate, the proportion of the trifunctional or more (meth)acrylate is 50% by mass or more with respect to the total mass of nonvolatile matter of the curable composition, an irregular wrinkle-like uneven structure is formed on the surface of the cured film, the root mean square gradient Sdq of the coating surface of the irregular wrinkle-like uneven structure as defined by ISO 25178 is less than 0.3, the unfolded interface area ratio Sdr of the coating surface of the irregular wrinkle-like uneven structure as defined by ISO 25178 is 3.0% or less, and the haze is 60% or less.

2. A film comprising a transparent substrate and a cured film provided on the surface of the transparent substrate, wherein the cured film is a cured product of a curable composition, an irregular wrinkle-like uneven structure is formed on the surface of the cured film, the root mean square gradient Sdq of the coating surface of the irregular wrinkle-like uneven structure as defined by ISO 25178 is less than 0.3, the unfolded interface area ratio Sdr of the coating surface of the irregular wrinkle-like uneven structure as defined by ISO 25178 is 3.0% or less, the maximum distance Sz from the highest point to the lowest point of the uneven surface of the irregular wrinkle-like uneven structure as defined by ISO 25178 is 6.0 μm or less, and the haze is 60% or less.

3. A film comprising a transparent substrate and a cured film provided on the surface of the transparent substrate, wherein the cured film is a cured product of a curable composition, the curable composition contains a difunctional (meth)acrylate, a trifunctional to hexafunctional (meth)acrylate, and a heptafunctional or more (meth)acrylate, the proportion of the heptafunctional or more (meth)acrylate is 50% by mass or more with respect to the total mass of nonvolatile matter of the curable composition, and an irregular wrinkle-like uneven structure is formed on the surface of the cured film.

4. The film according to any one of claims 1 to 3, wherein the cured product is a cured product obtained by curing the curable composition by irradiation with vacuum ultraviolet light.

5. The film according to any one of claims 1 to 3, wherein the curable composition may further contain particles, and the proportion of the particles is 0 to 30% by mass with respect to the total mass of the nonvolatile content of the curable composition.

6. The film according to claim 5, wherein the average particle size of the particles is 0.01 to 30 μm.

7. The film according to claim 3, wherein the haze is 60% or less.

8. The film according to any one of claims 1 to 3, wherein the 60° gloss of the surface of the cured film is 10 or more.

9. The film according to claim 3, wherein the root mean square gradient Sdq of the coating surface having the irregular wrinkle-like uneven structure as defined in ISO 25178 is less than 0.

3.

10. The film according to claim 3, wherein the unfolded interface area ratio Sdr of the coating surface having an irregular wrinkle-like uneven structure as defined in ISO 25178 is 3.0% or less.

11. The film according to any one of claims 1 to 3, wherein the Scale area fractal complexity (Sac) of the irregular wrinkled uneven structure, as defined in ISO 25178, is 5.0 or less.

12. The film according to any one of claims 1 to 3, wherein the arithmetic mean roughness Ra of the roughness curve elements of the irregular wrinkle-like uneven structure according to JIS B0601:2013 is 1.0 μm or less.

13. The film according to any one of claims 1 to 3, wherein the inclination angle θα of the roughness curve element of the irregular wrinkle-like uneven structure according to JIS B0601:2013 is 6.0° or less.

14. The film according to claim 1 or 3, wherein the maximum distance Sz from the highest point to the lowest point of the uneven surface defined in ISO 25178 for the irregular wrinkle-like uneven structure is 6.0 μm or less.

15. The film according to any one of claims 1 to 3, wherein the transparent substrate is at least one selected from the group consisting of cycloolefin polymer film, polyethylene terephthalate film, polyacrylic polymer film, and triacetylcellulose film.

16. A polarizing plate having the film according to any one of claims 1 to 3.

17. A liquid crystal display having the film described in any one of claims 1 to 3.

18. An image display module comprising an image display device and a protective member, wherein the protective member is a film according to any one of claims 1 to 3, and the image display device is disposed on the transparent substrate side.

19. A method for manufacturing a film using a curable composition, wherein the curable composition contains at least a difunctional (meth)acrylate and a trifunctional or more (meth)acrylate, the proportion of the trifunctional or more (meth)acrylate is 50% by mass or more with respect to the total mass of nonvolatile matter of the curable composition, and the curable composition is cured by irradiating it with vacuum ultraviolet light after applying the curable composition to a transparent substrate.

20. A method for manufacturing a film using a curable composition, wherein the curable composition contains a difunctional (meth)acrylate, a trifunctional to hexafunctional (meth)acrylate, and a heptafunctional (meth)acrylate, the proportion of the heptafunctional (meth)acrylate is 50% by mass or more with respect to the total mass of the nonvolatile content of the curable composition, and the curable composition is cured by irradiating it with vacuum ultraviolet light after applying the curable composition to a transparent substrate.

21. A curable composition containing a bifunctional (meth)acrylate, a trifunctional to hexafunctional (meth)acrylate, and a heptafunctional or more functional (meth)acrylate, wherein the proportion of the heptafunctional or more functional (meth)acrylate is 50% by mass or more of the total mass of the nonvolatile content of the curable composition.

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