TW201800263A - Decorative film, image display device, touch panel, and method of producing decorative film - Google Patents

Abstract

A decorative film, applications for same and a manufacturing method for same, the decorative film comprising a polyester film, a decorative layer, and a hard coating layer, wherein the curl value of the decorative film generated when heat history is applied at a temperature of 150 DEG C for 30 minutes to a decorative film piece that is 50mm long and 50mm wide is not more than 5mm.

Description

Decorative film, image display device, touch panel, and method for manufacturing decorative film

The present disclosure relates to a method for manufacturing a decorative film, an image display device, a touch panel, and a decorative film.

Cathode tube display device, plasma display, electroluminescence display, fluorescent display display, field emission display, and liquid crystal display device (Liquid Crystal Display (LCD)) In various displays such as image display devices or small terminals such as smartphones and tablet terminals equipped with a touch panel, a hard coating is provided on a support containing resin as a main component. In the case of a layer and a laminated film having a decorative layer. The hard coat layer is usually provided for the purpose of preventing damage to the image display surface. The laminated film having a decorative layer is configured for the purpose of applying various designs by hiding wirings arranged in the device body on the image display surface and the like. In particular, in a small terminal equipped with a touch panel, a finger is used to directly touch the screen or a touch pen is used to touch the screen. Therefore, in order to effectively prevent the damage of the film, the wear resistance of the image display surface is required to be good.

In the case where the hardness of the hard coating layer is increased to produce a hard film, when a decorative film having a hard coating layer and a decorative layer is processed and fixed on a display, the size of the decorative film is determined by pressing. Make adjustments. The polyester film substrate, the hard hard coating layer, and the decorative layer containing a decorative colorant having different physical properties from the hard coating layer have different mechanical strengths and extensibility. Therefore, during the stamping process, interlayer peeling may occur. Or cracks can occur in hard hard coatings.

For example, as a hard coating film for an image display surface that has a moderate surface hardness and can be used in combination with a decorative layer, a hard coating film having an acrylic resin base material and having specific physical property values has been proposed (for example, refer to Japanese Patent Laid-Open Publication 2014-109712). In addition, a cover film for an image display surface has been proposed. The cover film has a decorative layer on the surface of a resin substrate such as a polycarbonate substrate and a polyethylene terephthalate substrate, and no decorative layer is provided. The area is covered by a hard coat layer, which can be manufactured inexpensively and can be formed as a thin layer (for example, refer to Japanese Patent Laid-Open No. 2014-35493). A surface coating material for a frame containing a resin layer containing particles and having a specific haze value and Martens hardness is proposed, and it is described that a good feel is provided to the surface (for example, refer to Japanese Patent Laid-Open No. 2013- 244624).

[Problems to be Solved by the Invention] However, according to research by the present inventors, it is known that, in a decorative film having a resin substrate, a decorative layer, and a hard coat layer, the physical properties of each constituent element are greatly different, and thus various kinds of components are produced. problem. For example, in the film described in Japanese Patent Laid-Open No. 2014-109712, if the surface hardness of the hard coat layer is increased, only the hard coat layer becomes hard, and the adhesiveness with the adjoining decorative layer and the resin substrate may be deteriorated. reduce. Furthermore, due to the physical properties when subjected to a thermal history, when the decorative film is stamped into an appropriate shape, peeling between the hard coat layer and the resin substrate or the decorative layer may occur, or cracks may occur during the stamping process. Or shattered. In addition, in Japanese Patent Laid-Open No. 2014-109712, as a comparative example, the use of a polyethylene terephthalate substrate instead of an acrylic resin substrate is disclosed, but it is described at the time of image display Rainbow-like unevenness and blackout caused by the phase difference of incident light are generated. That is, it is considered that a hard coating film using a polyethylene terephthalate substrate has a problem in optical characteristics. Therefore, in the technology described in Japanese Patent Laid-Open No. 2014-109712, the use of a polyester film is not envisaged. On the substrate.

In addition, in the cover film described in Japanese Patent Laid-Open No. 2014-35493, a region having no decorative layer is covered with a hard coating layer, so the adhesion between the hard coating layer and the decorative layer is improved. However, like the film described in Japanese Patent Application Laid-Open No. 2014-109712, the cover film described in Japanese Patent Laid-Open No. 2014-35493 is subject to heat from the resin substrate and the hard coat layer. In the case of physical processes, peeling between the hard coat layer and the resin substrate may occur, or cracks or chipping may occur during press processing.

Japanese Patent Application Laid-Open No. 2013-244624 discloses that the covering material for a frame is coated on the surface of the frame with inline coating as a premise. Therefore, it is not envisaged to use the coating material when mounting on the frame. Press processing to make the size uniform. Since the coating material described in Japanese Patent Laid-Open No. 2013-244624 has a resin layer containing particles, it has a soft touch when it is touched with a finger. However, as described above, stamping and the like are not envisaged. However, even when stamping is performed, the resin layer contains particles and the stamping adaptability is low, which may cause cracks during stamping.

An object of one embodiment of the present invention is to provide a decorative film having suppressed cracks and chipping during press processing and excellent in abrasion resistance, an image display device including the decorative film, and a touch panel. Another object of another embodiment of the present invention is to provide a method for producing a decorative film, which can produce a decorative film in which occurrence of chipping during press processing is suppressed and which is excellent in abrasion resistance. [Means for solving problems]

This disclosure includes the following embodiments. <1> A decorative film comprising a polyester film, a decorative layer, and a hard coat layer. The decorative film is produced by applying a thermal history of 150 ° C and 30 minutes to a film with a length of 50 mm and a width of 50 mm. The curl value of the film is 5 mm or less.

<2> The decorative film according to <1>, wherein the decorative film has a decorative layer in at least a part of the entire area of the decorative film in a plan view. <3> The decorative film according to <1> or <2>, wherein the in-plane retardation Re of the polyester film at a measurement wavelength of 589 nm is in a range of 3000 nm to 50000 nm.

<4> A decorative film comprising a polyester film, a decorative layer, and a hard coat layer. When the polyester film is given a thermal history of 150 ° C and 30 minutes, one direction and one direction in the plane of the polyester film The thermal shrinkage ratios in all directions orthogonal to each other in the plane were 3.0% or less. <5> The decorative film according to <4>, wherein the polyester film is a uniaxially oriented polyester film.

<6> The decorative film according to <4> or <5>, wherein the decorative layer is disposed on one side of the polyester film, and the hard coat layer is disposed on the polyester film on the side opposite to the surface on which the decorative layer is disposed surface. <7> The decorative film according to any one of <4> to <6>, which has a decorative layer in at least a part of the entire area of the decorative film in a plan view. <8> The decorative film according to any one of <4> to <7>, wherein the thickness of the polyester film is 40 μm to 500 μm.

<9> The decorative film according to any one of <4> to <8>, wherein the in-plane retardation Re of the polyester film at a measurement wavelength of 589 nm is in a range of 3000 nm to 50000 nm. <10> The decorative film according to any one of <4> to <9>, wherein the in-plane retardation Re of the polyester film at a measurement wavelength of 589 nm is relative to the thickness direction of the polyester film at a measurement wavelength of 589 nm The ratio of the retardation Rth is in the range of 0.6 to 1.2. <11> The decorative film according to any one of <4> to <10>, which has an easy-adhesive layer on at least one surface of the polyester film.

<12> The decorative film according to any one of <4> to <11>, wherein the hard coat has a pencil hardness of H or more. <13> The decorative film according to any one of <4> to <12>, wherein the thickness of the hard coat layer is 5 μm or more. <14> The decorative film according to any one of <4> to <13>, wherein the hard coat layer includes at least a structure derived from a) below, a structure derived from b) below, c) below, and The following d) includes a structure derived from the following a) and a structure derived from the following b) of 15% to 70% by mass with respect to the total solid content of the hard coat layer. 0.1 to 10% by mass of the following c), 0.1 to 10% by mass of the following d); a) having an alicyclic epoxy group and an ethylenically unsaturated double bond in the molecule A compound having a molecular weight of 300 or less, b) a compound having three or more groups containing an ethylenically unsaturated double bond in the molecule, c) a radical polymerization initiator, and d) a cationic polymerization initiator.

<15> An image display device including an image display element and the decorative film according to any one of <1> to <14>, and having a decorative film on an outermost surface. <16> A touch panel including the decorative film according to any one of <1> to <14>, and having a decorative film on an outermost surface.

<17> A method for producing a decorative film, comprising: a polyester film forming step; a decorative layer forming step for forming a decorative layer on at least a part of one surface of the polyester film; and a hard coat layer forming step for polyester A hard coat layer is formed on at least one side of the film, and the polyester film forming step includes a lateral stretching step using a tenter having a plurality of clamps that move along a pair of rails provided on both sides of the film conveying road, respectively. Type stretching device, in a state where the unstretched polyester film is held by a clamp, the stretching is performed in a direction orthogonal to the film conveying road; the heat-fixing step is performed by heating the polyester film after the transverse stretching Heat fixing; and a heat relaxation step, which heats the polyester film after the heat fixing step, and reduces the length of the polyester film in the film transport direction and the direction orthogonal to the film transport direction, and in the heat relaxation step The relaxation rate in the film transport direction of the polyester film after the heat fixing step is set to 0.1% to 7%, and the relaxation rate in a direction orthogonal to the film transport direction is set to 0.1% to 7%. To And forming the conveyance direction with respect to a direction perpendicular to the film conveying direction and imparting at temperature 150 ℃, thermal shrinkage of the thermal history of the polyester film were 30 minutes of 3.0% or less.

<18> The method for producing a decorative film according to <17>, wherein the length of the shrinking polyester film in the heat-relief step in a direction orthogonal to the film transport direction includes reducing the length of the polyester film provided on both sides of the film transport road The distance between the pair of rails in the heat-relieving step is to reduce the length in the film transport direction of the polyester film by reducing the interval between the plurality of clamps that are moved. <19> The method for producing a decorative film according to <17> or <18>, wherein reducing the length in the film conveying direction of the polyester film in the heat relaxation step includes applying tension to the film conveying direction of the polyester film and Reduce the length while conveying while heating.

<20> The method for producing a decorative film according to any one of <17> to <19>, wherein the conveying tension of the polyester film in the heat-relaxing step is 10 N / m width to 80 N / m width. The film surface temperature of the ester film during heating is 110 ° C to 190 ° C, and the heat treatment time is 10 seconds to 600 seconds. When the polyester film is cooled after reducing the length of the polyester film, the film surface temperature of the polyester film is 70 ° C ± The cooling rate in the range of 20 ° C is 100 ° C / min to 2000 ° C / min. [Effect of the invention]

According to one embodiment of the present invention, it is possible to provide a decorative film with suppressed occurrence of chipping during press processing and excellent scratch resistance, an image display device including the decorative film, and a touch panel. Moreover, according to another embodiment of this invention, the manufacturing method of the decorative film which can suppress the occurrence of chipping at the time of a press process, and can provide the decorative film excellent in abrasion resistance can be manufactured.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be performed based on a representative embodiment or a specific example, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value. In addition, when a unit is added to one of the numerical values described before and after "~", it means that the entire numerical range is the same unit. In this specification, "(meth) acrylfluorenyl" means either or both of "acrylfluorenyl" and "methacrylfluorenyl", and "(meth) acrylate" means "acrylate "And" methacrylate ", and" (meth) acryl "refers to either or both of" acryl "and" methacryl ". In this specification, the room temperature means 25 ° C unless otherwise specified.

[Decorative film] The decorative film according to the first embodiment of the present invention is a decorative film having a polyester film, a decorative layer, and a hard coat layer, and a temperature of 150 ° C is applied to the film length of the decorative film having a length of 50 mm and a width of 50 mm. The curl value of the decorative film generated during a 30-minute thermal history is 5 mm or less. In addition, "the thermal history provided at 150 degreeC for 30 minutes" means that the decorative film is left to stand in a temperature environment of 150 degreeC for 30 minutes, and is heated.

A method for measuring the curl value of the decorative film will be described with reference to FIG. 1. First, the decorative film was cut out to a length of 50 mm and a width of 50 mm to produce a film (hereinafter referred to as a decorative film) 10 having a length of 50 mm and a width of 50 mm as a decorative film for a test piece. FIG. 1A is a plan view showing the cut-out decorative film sheet 10. In the plan view of the decorative film 10, a measurement target portion of the curl value is schematically indicated by a mark. The measurement target portion was set at four corner portions of the cut out decorative film sheet 10 and four center portions of each of the square pieces, for a total of eight. The obtained decorative film sheet 10 shown in FIG. 1A was put into a heating furnace at a temperature of 150 ° C. for 30 minutes. Then, after conditioning for 8 hours in an environment with a temperature of 25 ° C. and a humidity of 60%, as shown in FIG. 1B, the decorative film 10 is placed on a flat place 12, and the surface of the flat place 12 is used as a measurement reference surface. . The distance between the reference surface and the measurement target site in the decorative membrane 10 (indicated by an arrow H in FIG. 1B), that is, the measurement target site in the vertical line drawn from the measurement target site of the decorative membrane 10 to the reference plane and the reference The distance between the faces was measured as a curl value. FIG. 1B is a side view showing a state in which the decorative film 10 is placed on a flat place 12. In FIG. 1B, a distance indicated by an arrow H is set as a curl value. When the decorative film 10 is curled into a convex shape with respect to the flat portion 12 as shown in FIG. 1C after heating, the decorative film 10 is inverted and arranged in a concave shape, that is, in a state shown in FIG. 1B for measurement. The curl value of the decorative film sheet 10 as a measurement target is set to the average value of the curl value measured in the eight measurement target parts of the previously described decorative film sheet.

In the decorative film of this embodiment, the curl of the decorative film having undergone the thermal history described above is 5 mm or less, preferably 3 mm or less, and more preferably 2 mm or less. In the case where the curl of the decorative film measured at the above-mentioned upper limit exceeds 5 mm, when the decorative film is press-added, the polyester film and the decorative layer are easily peeled off, which is not satisfactory.

The decorative film according to the second embodiment of the present invention is a decorative film having a polyester film, a decorative layer, and a hard coat layer. When the polyester film is given a thermal history of 150 ° C and 30 minutes, the in-plane of the polyester film The thermal contraction rate in one direction and a direction orthogonal to the one direction in the plane are both 3.0% or less.

Hereinafter, an example of the embodiment of the present disclosure will be referred to as a decorative film of the first embodiment, and an example of another embodiment will be referred to as a decorative film of the second embodiment. The constituent elements will be described. In addition, in this specification, when referring to both the 1st embodiment and the 2nd embodiment, it may be collectively called "the embodiment of this indication."

[Polyester Film] The decorative films of the first and second embodiments have a polyester film as a base material. As one of the methods for achieving the condition that the decorative film disclosed by the present invention is crimped to 5 mm or less in the thermal history described above, a polyester film having a small thermal shrinkage rate can be used as a substrate. Examples of the polyester film having a small thermal shrinkage include a polyester film which, when used in the decorative film of the second embodiment described above, imparts a thermal history of 150 ° C and 30 minutes to the polyester film, The thermal shrinkage of the polyester film in one direction and a direction orthogonal to the one direction in the plane were both 3.0% or less. In addition, other methods include increasing the thickness of the polyester film as the base material; extending the polyester film at a high magnification to increase the modulus of elasticity of the film used for the base material; and these methods are also effective.

As the polyester film used in the decorative film of the first embodiment, when the polyester film is provided with a thermal history of 150 ° C. and 30 minutes, it is preferably one direction in the plane of the polyester film and the first direction of the polyester film. The polyester film has a thermal shrinkage of 3.0% or less in the directions orthogonal to each other in the plane. In the decorative film of the second embodiment, when the polyester film is provided with a thermal history of 150 ° C. and 30 minutes as a base material, one direction in the plane of the polyester film and one direction orthogonal to the direction in the plane are provided. The polyester film with a thermal shrinkage ratio in all directions of 3.0% or less.

<Characteristics of Polyester Film> (Heat Shrinkage Rate) The polyester film that can be used in the decorative film of the present disclosure is preferably in one direction in the plane, for example, the film conveying direction (machine direction), which is hereinafter sometimes referred to as "MD direction") and a direction orthogonal to one direction (for example, when one direction is set to "MD direction", the direction orthogonal to the film conveying direction (transverse direction), hereinafter sometimes called "TD direction")) In both directions, the heat shrinkage rate is 3.0% or less when the following thermal history is given. The decorative film of the second embodiment has the following In the case of thermal history, the polyester film has a thermal contraction rate of 3.0% or less in one of the directions below and the direction orthogonal to the direction in the plane. The thermal history at the time of measuring the thermal contraction rate of a polyester film was standing still at the temperature of 150 degreeC for 30 minutes. Hereinafter, the uniaxially stretched polyester film which is a preferable aspect as a base material in the decorative film of this disclosure is demonstrated as an example. In one direction of the polyester film and the direction orthogonal to the one direction, the thermal shrinkage of the polyester film after a thermal history at a temperature of 150 ° C for 30 minutes is preferably 3.0% or less, more preferably 1.5% or less, and even more preferably It is 0.5% or less. By using a polyester film having a thermal shrinkage of 3.0% or less measured under the conditions described, the thermal stability of the polyester film as a base material is further improved, and wrinkles during the production of a decorative film can be more effectively suppressed. And the occurrence of interlayer peeling and chipping when the decorative film is pressed.

The absolute value of the difference between the thermal shrinkage rate of the polyester film in one direction in the plane of the polyester film and the direction orthogonal to the one direction in the plane of the polyester film is preferably 0.6%. Hereinafter, it is more preferably 0.4% or less, and still more preferably 0.3% or less. The difference in the thermal shrinkage of the polyester film in two directions orthogonal to each other in the plane is small, and the physical properties of the polyester film become more uniform. When other layers are laminated on the polyester film to make a decorative film, It is possible to more effectively suppress the occurrence of wrinkles of the decorative film during the press processing or when the decorative film after the press processing is fixed on the member.

In this specification, the thermal contraction rate under the conditions of a temperature of 150 ° C. and 30 minutes as the thermal history, that is, the thermal contraction rate of a film after heating at 150 ° C. for 30 minutes is sometimes referred to as “thermal contraction rate (150 ° C, 30 minutes) ". A method for measuring the thermal shrinkage will be described. For the test piece M cut into a polyester film with a width of 30 mm and a length of 120 mm in one direction in the plane, two reference lines were cut in advance in the longitudinal direction at positions where the distance became 100 mm. After leaving the sample piece M in a heating oven at 150 ° C. for 30 minutes under no tension, the sample piece M was cooled to room temperature, and the interval between the two reference lines was measured. The measured interval after the treatment is A [mm]. The value [%] calculated from the interval of 100 mm before the treatment and the interval of A mm after the treatment using the formula "100 × (100-A) / 100" is set as the heat shrinkage rate of the sample piece M (150 ℃, 30 minutes). In the measurement, three specimens were measured at three locations in each direction, and the arithmetic average of the measurement results at a total of nine locations was set as the measurement value. For example, when one direction is set to the MD direction, the heat shrinkage in the MD direction is also referred to as the MD heat shrinkage, and the ratio thereof is referred to as the MD heat shrinkage rate. Therefore, the thermal contraction rate in the direction orthogonal to the film width direction when the polyester film is manufactured becomes the contraction rate in the film transport direction, and can be referred to as the MD thermal contraction rate.

In this specification, the thermal contraction rate (150 ° C, 30 minutes) in a direction orthogonal to the previously described one direction after standing at 150 ° C for 30 minutes is defined as follows. When measuring the thermal shrinkage in a direction orthogonal to the one direction described, a polyester resin film cut into a width of 30 mm and a length of 120 mm in the direction orthogonal to the one direction described was used as a sample. For the sheet M, two reference lines were cut into the sample sheet M in advance in the longitudinal direction at intervals of 100 mm. After leaving the sample piece M in a heating oven at 150 ° C. for 30 minutes under no tension, the sample piece M was cooled to room temperature, and the interval between the two reference lines was measured. The measured interval after the treatment is A [mm]. The value [%] calculated from the interval of 100 mm before the treatment and the interval of A mm after the treatment using the formula "100 × (100-A) / 100" is set to be positive in the one direction of the sample piece M. Thermal shrinkage in the direction of intersection (150 ° C, 30 minutes). For example, when one direction is set to the MD direction, the direction orthogonal to the one direction is set to the TD direction, and the thermal contraction thereof may be referred to as a TD thermal contraction, and the ratio thereof may be referred to as a TD thermal contraction rate.

The polyester film having a thermal shrinkage (150 ° C, 30 minutes) of 3.0% or less as described above is preferably a uniaxially oriented polyester film. The unstretched polyester film formed by the melt-forming or solution-forming method is laterally stretched, heat-fixed, and heat-relieved by a method described later, thereby easily obtaining a polyester film having the preferable thermal shrinkage ratio as described above.

(Thickness) The thickness of the polyester film is preferably 40 μm to 500 μm, more preferably 60 μm to 400 μm, and even more preferably 80 μm to 300 μm. When the thickness of the polyester film is within the above range, the decorative film has sufficient rigidity and can be suitably used as a substitute material for glass, and it is possible to suppress a decrease in punchability and a decrease in operability due to excessive rigidity. In addition, when the thickness of the polyester film is within the above range, the dimensional stability of the decorative film becomes better. The thickness of the polyester film can be measured using, for example, a contact-type film thickness meter. In the measurement, 50 points were sampled in one direction of the polyester film and the direction orthogonal to the one direction, and the average thickness of the measured values of the thicknesses at these points was determined to be the thickness of the polyester film.

-Re (retardation in the film plane)-The polyester film used in the decorative film of the present disclosure preferably has a retardation Re in the film plane at a measurement wavelength of 589 nm, which is 4000 nm to 50000 nm. Hereinafter, as long as there is no particular limitation, the retardation Re in the film plane in this specification means a value at a measurement wavelength of 589 nm. If the Re of the polyester film is 3,000 nm or more, rainbow-like unevenness is not easily recognized. If it is 50,000 nm or less, the required film thickness does not become excessively thick, rigidity can be suppressed to be excessive, and handling becomes easy. From the viewpoint, the Re of the polyester film is more preferably 5000 nm to 40,000 nm, and even more preferably 7000 nm to 33000 nm.

-Re / Rth- In addition, it is preferable that the polyester film has a ratio (Re / Rth) of retardation in the film plane at the measurement wavelength of 589 nm to retardation Rth in the thickness direction of the film at the measurement wavelength of 589 nm from 0.6 to 1.2. . If the Re / Rth of the polyester film is 0.6 or more, rainbow-like unevenness is not easily recognized, and if it is 1.2 or less, the film is not easily brittle. Hereinafter, unless otherwise specified, the retardation Rth in the film thickness direction in this specification means a value at a measurement wavelength of 589 nm. From such a viewpoint, the Re / Rth of the polyester film is more preferably 0.7 to 1.15, and even more preferably 0.8 to 1.1.

The retardation Rth in the thickness direction of the polyester film is preferably 3000 nm to 80,000 nm, more preferably 4000 nm to 60,000 nm, and even more preferably 6000 nm to 40,000 nm. If the Rth of the polyester film is 3,000 nm or more, it is easy to make a film. If the Rth of the polyester film is 80,000 nm or less, when a hard coat layer using a polyester film is applied to, for example, a display screen of an image display device, the screen is unlikely to occur. Rainbow-like unevenness is preferred.

The retardation Re in the film surface of the polyester film is represented by the following formula (1). Formula (1): Re = (nx-ny) × y _{1 In} formula (1), nx is a refractive index in one direction of the plane of the polyester film, and ny is orthogonal to one direction in the plane of the polyester film. In the direction of the refractive index, y ₁ is the thickness of the polyester film.

The retardation Rth in the thickness direction of the polyester film of this embodiment is represented by the following formula (2). Formula (2): Rth = {(nx + ny) / 2-nz} × y _{1 In} formula (2), nz is a refractive index in the thickness direction of the polyester film.

The Nz value of the polyester film is represented by the following formula (3). Equation (3): Nz = (nx-nz) / (nx-ny)

In this specification, Re, Rth, and Nz at a wavelength λ nm can be measured as follows. Using two polarizing plates, the orientation axis direction of the polyester film was determined and set as one direction in the plane. A 4 cm × 2 cm rectangle was cut out at a position orthogonal to the alignment axis direction as a measurement sample. With respect to the obtained measurement sample, an orthogonal biaxial refractive index (nx, ny) was obtained using an Abbe refractometer (NAR-4T, manufactured by Atago, measuring wavelength is 589 nm), and The refractive index (nz) in the thickness direction, and the absolute value (| nx-ny |) of the biaxial refractive index difference is set to the anisotropy (Δnxy) of the refractive index. The thickness y ₁ (nm) of the polyester film was measured using an electric micrometer (manufactured by Feinpruf, Miritoron 1245D), and the unit was converted to nm. Re, Rth, and Nz were calculated from the measured values of nx, ny, nz, and y ₁ , respectively.

The Re and Rth at the measurement wavelength of 589 nm can be determined by the type of polyester resin used in the film, the amount of polyester resin and additives, the addition of a retarder, the film thickness of the film, and the direction and extension of the film. Rate and so on. The method of controlling the Re and Re / Rth of the polyester film to their respective ranges is not particularly limited. As a method of controlling Re and Re / Rth of a polyester film, the stretching method is mentioned, for example.

(Constituent Material, Layer Structure, and Surface Treatment of Polyester Film) The polyester film used in the decorative film of the present disclosure includes a polyester resin. The content ratio of the polyester resin in the entire polyester film is usually 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more. The polyester film may be a single-layer film having a layer containing a polyester resin as a main component, or a multilayer film having at least one layer containing a polyester resin as a main component. In addition, the polyester film may be surface-treated on both sides or one side of the film. The surface treatment may be corona treatment, saponification treatment, heat treatment, surface modification by ultraviolet irradiation, electron beam irradiation, or the like, or film formation by coating or vapor deposition of polymer compounds, metals, and the like.

The polyester film may have an easy adhesion layer on at least one side. The thickness of the easy-adhesive layer contained in the polyester film is preferably 30 nm to 300 nm, more preferably 40 nm to 200 nm, and even more preferably 50 nm to 150 nm. If the thickness of the easy-adhesion layer is 30 nm or more, it is easy to obtain a cushioning effect brought by the easy-adhesion layer, and it is possible to suppress the vertical stress of the shear plane and the excessive increase of the shear stress of the shear plane. In addition, if the thickness of the easy-adhesion layer is 300 nm or less, the cushioning effect of the easy-adhesion layer will not be too strong, and the vertical stress on the shear plane and the shear stress on the shear plane can be suppressed from being excessively reduced.

More preferably, the easily-adhesive layer contains particles, and the height of the particles protruding from the surface of the easily-adhesive layer is equal to or greater than the film thickness of the easily-adhesive layer. The height of the particles protruding from the surface of the easy-adhesive layer was an average of 5 points in the 1-mm square easy-adhesive layer. If the height of the particles contained in the easy-adhesive layer and the protrusion of the particles from the surface of the easy-adhesive layer is smaller than the film thickness of the easy-adhesive layer (preferably a coating layer), the smoothness is reduced and wrinkles are easily generated. The type of particles that can be contained in the easy-adhesion layer is not particularly limited. Specific examples include silicon dioxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, alumina, and oxidation. Particles such as titanium and zirconia are preferably silicon dioxide, aluminum oxide, titanium oxide, and zirconia. In addition, heat-resistant organic particles described in Japanese Patent Laid-Open No. 59-5216, Japanese Patent Laid-Open No. 59-217755, and the like can also be used. Examples of other heat-resistant organic particles include particles such as a thermosetting urea resin, a thermosetting phenol resin, a thermosetting epoxy resin, and a benzoguanamine resin. The particle diameter is preferably a particle diameter in which the height of the particles protruding from the surface of the easily-adhesive layer is equal to or greater than the film thickness of the easily-adhesive layer. It is preferred to use particles adjusted by the primary average particle diameter, but particles may be aggregated such that the height of the particles protruding from the surface of the easily-adhesive layer is greater than the film thickness of the easily-adhesive layer as a result. In the case of aggregated particles, the height of the particles protruding from the surface of the easily-adhesive layer can be confirmed by measuring the secondary average particle diameter.

(1-1) Polyester resin As the polyester resin contained in the polyester film, for example, a polyester resin having a composition of [0042] in WO2012 / 157662 can be preferably used. As specific polyester resins, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate, PBT), polycyclohexanedimethylene terephthalate (PCT), etc., but in terms of cost and heat resistance, PET and PEN are more preferred, and PET is more preferred. Furthermore, as far as PEN is concerned, Re / Rth becomes slightly smaller. The polyester resin is preferably polyethylene terephthalate. In addition, polyethylene naphthalate can also be preferably used, for example, polyethylene naphthalate described in Japanese Patent Laid-Open No. 2008-39803 can be preferably used.

Polyethylene terephthalate is a polyester having a structural unit derived from terephthalic acid as a dicarboxylic acid component and a structural unit derived from ethylene glycol as a diol component. Ear percentage or more may be ethylene terephthalate, and may also contain a structural unit derived from other copolymerization components. Examples of other copolymerization components include isophthalic acid, p-β-oxyethoxybenzoic acid, 4,4'-dicarboxydiphenyl, 4,4'-dicarboxybenzophenone, and bis (4 -Carboxyphenyl) dicarboxylic acid components such as ethane, adipic acid, sebacic acid, sodium isophthalate-5-sulfonate, 1,4-dicarboxycyclohexane, propylene glycol, butanediol, neopentyl Diol components such as glycol, diethylene glycol, cyclohexanediol, ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol. These dicarboxylic acid components or diol components can be used in combination of two or more kinds as needed. The carboxylic acid component or the diol component may be used in combination with a hydroxycarboxylic acid such as p-hydroxybenzoic acid. As other copolymerization components, a small amount of a dicarboxylic acid component and / or a diol component containing an amine bond, a urethane bond, an ether bond, a carbonate bond, or the like may be used. As a method for producing polyethylene terephthalate, a so-called direct polymerization method in which terephthalic acid reacts directly with ethylene glycol and other dicarboxylic acids and / or other diols as necessary, can be applied. Any production method such as a so-called transesterification reaction method in which a dimethyl terephthalate is subjected to a transesterification reaction with ethylene glycol, and dimethyl esters of other dicarboxylic acids and / or other diols as necessary.

(1-2) Physical properties of polyester resin (1-2-1) Intrinsic viscosity IV (Intrinsic Viscosity) of polyester resin is preferably 0.5 or more and 0.9 or less, more preferably 0.52 or more and 0.8 or less, and even more It is preferably 0.54 or more and 0.7 or less. In order to keep IV in the range described above, when synthesizing the polyester resin, in addition to the melt polymerization described later, solid phase polymerization may be used in combination.

(1-2-2) Acetaldehyde content The acetaldehyde content of the polyester resin is preferably 50 ppm or less. It is more preferably 40 ppm or less, and particularly preferably 30 ppm or less. Acetaldehyde may easily undergo a condensation reaction with each other, and generate water as a side reactant. The hydrolysis of the polyester proceeds with the generated water. The lower limit of the acetaldehyde content is practically about 1 ppm. In order to set the acetaldehyde content within the above range, methods such as: keeping the oxygen concentration in each step such as melt polymerization and solid phase polymerization during resin production low, and maintaining the oxygen concentration during resin storage and drying It is low; reduces the thermal history of the resin due to the extruder, the melt piping, the mold, etc. during the production of the film; adjusts it so that it does not locally receive strong shear due to the screw configuration of the extruder during melting condition.

(1-3) Catalysts Sb-based catalysts, Ge-based catalysts, Ti-based catalysts and / or Al-based catalysts are used in the polymerization of polyester resins, preferably Sb-based catalysts, Ti-based catalysts and The Al-based catalyst is more preferably an Al-based catalyst. That is, the polyester resin used as the raw material resin of the polyester film is preferably a resin polymerized using an aluminum catalyst. By using an Al-based catalyst, Re is more easily visualized than when using other catalysts (for example, Sb or Ti), and PET thinning can be achieved. That is, using an Al-based catalyst means that alignment is easier. The reason is speculated as follows. Compared with Sb-based catalysts or Ti-based catalysts, Al-based catalysts have lower reactivity (polymerization activity), slower reactions, and are less likely to generate by-products (diethylene glycol unit: DEG (Diethylene glycol)). As a result, regularity of PET is improved, alignment is easy, and Re is easily visualized.

(1-3-1) Al-based catalyst As the Al-based catalyst, those described in [0013] to [0148] of WO2011 / 040161 ([0021] to [0123] of US2012 / 0183761) can be used. Al-based catalyst, the contents described in these publications can be incorporated into the specification of this application. The method for producing a polyester resin by polymerization using an Al-based catalyst is not particularly limited, and specifically, it can be based on [0091] to [0094] of WO2012 / 008488 (US2013 / 0112271 [0144] ~ [0153]) to perform polymerization, and the contents described in these publications can be incorporated into the specification of this application. In addition, the Al-based catalyst can be based on, for example, [0052] to [0054], [0099] to [0104] in Japanese Patent Laid-Open No. 2012-122051 ([0045] to [0047], [0047] in [WO2012 / 029725] 0091] to [0096]), and the contents described in these publications can be incorporated into the description of this application. The amount of the Al-based catalyst as the amount of the Al element relative to the mass of the polyester resin is preferably 3 ppm to 80 ppm, more preferably 5 ppm to 60 ppm, and even more preferably 5 ppm to 40 ppm.

(1-3-2) Sb-based catalyst As the Sb-based catalyst, the Sb-based catalysts described in [0050] and [0052] to [0054] of Japanese Patent Laid-Open No. 2012-41519 can be used. The method for polymerizing a polyester resin using an Sb-based catalyst is not particularly limited, but specifically, the polymerization can be performed in accordance with [0086] to [0087] of WO2012 / 157662.

(1-4) Additive It is also preferable to add a known additive to the polyester film. Examples of well-known additives include ultraviolet absorbers, particles, lubricants, antiblocking agents, heat stabilizers, antioxidants, antistatic agents, lightfasteners, impact modifiers, lubricants, dyes, and pigments. Wait. However, since polyester films generally require transparency, it is preferable to limit the amount of additives to a minimum.

(1-4-1) Ultraviolet (UV) absorbent In order to prevent the liquid crystal of liquid crystal displays from being deteriorated by ultraviolet rays, a polyester film may also contain ultraviolet absorbers. The ultraviolet absorbent is a compound having an ultraviolet absorbing ability, and is not particularly limited as long as it is an ultraviolet absorbent that can withstand the heat added in the production step of the polyester film. As the ultraviolet absorber, there are an organic ultraviolet absorber and an inorganic ultraviolet absorber. From the viewpoint of transparency, an organic ultraviolet absorber is preferred. The ultraviolet absorber described in [0057] of WO2012 / 157662 or a cyclic imide-based ultraviolet absorber described later can be used.

The cyclic imide-based ultraviolet absorber is not limited to the following, and examples thereof include 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1 -Benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2- (1-naphthyl or 2-naphthyl) -3,1-benzoxazine 4-one, 2- (4-biphenyl) -3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2- M-nitrophenyl-3,1-benzoxazin-4-one, 2-p-benzylidenephenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl -3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazine- 4-keto, 2-p- (or m-) phthalimidinephenyl-3,1-benzoxazin-4-one, N-phenyl-4- (3,1-benzoxazine -4-keto-2-yl) phthalimide, N-benzylidene-4- (3,1-benzoxazin-4-one-2-yl) aniline, N-benzyl Fluorenyl-N-methyl-4- (3,1-benzoxazin-4-one-2-yl) aniline, 2- (p- (N-methylcarbonyl) phenyl) -3,1-benzene Benzoxazin-4-one, 2,2'-bis (3,1-benzoxazin-4-one), 2,2'-ethylidenebis (3,1-benzoxazin-4-one Ketone), 2,2'-tetramethylenebis (3,1-benzoxazin-4-one), 2,2'-decamethylenebis ( 3,1-benzoxazin-4-one), 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) [Moreover, also Called 2,2'-p-phenylenebis (3,1-benzoxazin-4-one)], 2,2'-m-phenylenebis (3,1-benzoxazine-4- Ketone), 2,2 '-(4,4'-diphenylene) bis (3,1-benzoxazin-4-one), 2,2'-(2,6-naphthyl or 1 , 5-naphthyl) bis (3,1-benzoxazin-4-one), 2,2 '-(2-methyl-p-phenylene) bis (3,1-benzoxazine- 4-ketone), 2,2 '-(2-nitro-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2'-(2-chloro-p-phenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 '-(1,4-cyclohexyl) bis (3,1-benzoxazin-4-one), 1, 3,5-tris (3,1-benzoxazin-4-one-2-yl) benzene, 1,3,5-tris (3,1-benzoxazin-4-one-2-yl) Naphthalene, 2,4,6-tris (3,1-benzoxazin-4-one-2-yl) naphthalene, 2,8-dimethyl-4H, 6H-benzo (1,2-d; 5,4-d ') bis (1,3) -oxazine-4,6-dione, 2,7-dimethyl-4H, 9H-benzo (1,2-d; 4,5-d ') Bis (1,3) -oxazine-4,9-dione, 2,8-diphenyl-4H, 8H-benzo (1,2-d; 5,4-d') bis (1 , 3) -oxazine-4,6-dione, 2,7-diphenyl-4H, 9H-benzo (1,2-d; 4,5-d ') bis (1,3) -oxa Azine-4,6-dione, 6,6'-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-bis (2-ethyl-4H, 3,1-benzoxazin-4-one), 6,6'-bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-methylenebis (2-phenyl-4H, 3, 1-benzoxazin-4-one), 6,6'-ethenylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-ethenyl Bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-butylenebis (2-methyl-4H, 3,1-benzoxazine- 4-ketone), 6,6'-butanebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-oxybis (2-methyl- 4H, 3,1-benzoxazin-4-one), 6,6'-oxybis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6 ' -Sulfofluorenylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-sulfofluorenylbis (2-phenyl-4H, 3,1-benzo Oxazin-4-one), 6,6'-carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-carbonylbis (2-phenyl- 4H, 3,1-benzoxazin-4-one), 7,7'-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7 '-Methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 7,7'-bis (2-methyl-4H, 3,1-benzoxazine -4-ketone), 7,7'-ethylidenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-oxybis (2-methyl) -4H, 3,1-benzo Oxazin-4-one), 7,7'-sulfonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-carbonylbis (2-methyl -4H, 3,1-benzoxazin-4-one), 6,7'-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7'- Bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,7'-methylenebis (2-methyl-4H, 3,1-benzoxazine-4 -Ketone), 6,7'-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), and the like.

Among these compounds, when considering the color tone, a benzoxazinone-based compound that is hardly yellowed can be suitably used. For example, a compound represented by the following formula (4) can be more suitably used.

Formula (4)

In the formula (4), R represents a divalent aromatic hydrocarbon group, and X ¹ and X ² are each independently a hydrogen atom or a functional group selected from the following, but are not necessarily limited to these.

Functional group group: alkyl, aryl, heteroaryl, halogen, alkoxy, aryloxy, hydroxyl, carboxyl, ester, nitro.

Among the compounds represented by the formula (4), 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) is particularly preferred.

The quantity of the ultraviolet absorber which can be contained in a polyester film is 10.0 mass% or less with respect to the whole film normally, Preferably it is the range of 0.3 mass%-3.0 mass%. When the ultraviolet absorbent is contained in an amount exceeding 10.0% by mass, there is a possibility that the functionality of the surface may be reduced due to the ultraviolet absorbent oozing out to the surface, the adhesiveness, and the like being reduced.

Moreover, when a polyester film has a laminated structure, it is preferable to have a structure of at least 3 layers, and it is preferable to mix | blend an ultraviolet absorber to an intermediate layer (layer other than an outermost layer). By blending the ultraviolet absorber in the intermediate layer, it is possible to prevent the ultraviolet absorber from oozing out to the surface of the film, and as a result, characteristics such as adhesiveness of the film can be maintained. For the preparation of the ultraviolet absorber, for example, the master batch method described in [0050] to [0051] of WO2011 / 162198 can be used.

(1-4-2) Other additives In polyester films, other additives can also be used. For example, additives described in [0058] of WO2012 / 157662 can be used, and the contents described in the bulletin can be incorporated into In this application specification.

(Production of polyester film) The polyester film is preferably produced by the following production method. The manufacturing method includes a lateral stretching step of using a tenter type stretching device having a plurality of jigs that move along a pair of rails provided on both sides of a film conveying road, and clamping unstretched polyester with the jigs. In the state of the film, the film is stretched in a direction orthogonal to the film transport road; the heat-fixing step is performed by heating the polyester film stretched in the lateral direction to heat-fix; After the polyester film is heated, the length of the film transport direction of the polyester film and the direction orthogonal to the film transport direction is reduced, and in the heat relaxation step, the polyester film after the heat fixing step is The reduction ratio of the length in the film conveying direction orthogonal to the film conveying direction, that is, the relaxation rate in the direction orthogonal to the film conveying direction is set to 0.1% to 7%, and the film of the heat-fixed polyester film is set. The relaxation rate in the conveying direction is set to 0.1% to 7%, thereby making it possible to produce a film shrinking direction and a direction orthogonal to the film conveying direction at a temperature of 150 ° C. for a thermal history of 30 minutes when given a thermal history of 30 minutes. Rates are 3.0% or less polyester film suitable as a base of a decorative film. Here, the "unstretched polyester film" refers to a polyester film having a refractive index of 1.590 or less in both MD and TD. For example, although a micro-elongation is performed on MD, the refractive index of MD and TD are both 1.590 or less. Polyester film and the like are also included in the unstretched polyester film. Hereinafter, as a preferable aspect of the method for manufacturing a polyester film, a case where a uniaxially oriented polyester film is manufactured by forming an unstretched polyester film by melt extrusion and stretching in the lateral direction will be described.

<Melting and Kneading> It is preferable that the unstretched polyester film is melt-extruded into a polyester resin and formed into a film shape. Preferably, the polyester resin or the master batch of the polyester resin and additives produced by the master batch method is dried to a moisture content of 200 ppm or less, and then introduced into a uniaxial or biaxial extruder and Let it melt. In order to suppress the decomposition of the polyester resin in the extruder, it is also preferable to perform melting in nitrogen or vacuum. The detailed conditions can be referred to, for example, [0051] to [0052] of Japanese Patent No. 4962661 ([0085] to [0086] of US2013 / 0100378), and implemented in accordance with these publications. The contents can be incorporated into the specification of this application. Furthermore, in order to improve the delivery accuracy of the molten resin (melt), it is also preferable to use a gear pump. It is also preferable to use a filter having a pore diameter of 3 μm to 20 μm to remove foreign matter.

<Extrusion or co-extrusion> It is preferable to extrude a melt containing a melt-kneaded polyester resin from a die, and it can be extruded in a single layer or extruded in multiple layers (coextrusion). . When extruded in multiple layers, for example, a layer containing an ultraviolet absorbent (UV agent) and a layer not containing an ultraviolet absorbent can be laminated to suppress the bleeding of the UV agent and suppress the deterioration of the polarizing element caused by the UV agent. From a viewpoint, it is preferable to have a three-layer structure with a UV agent in the inner layer. When the UV agent oozes out, the UV agent on the surface of the film is sometimes transferred to the roller in contact with the film during the manufacturing process of the film, which increases the coefficient of friction between the film and the roller and easily causes scratches, which is not good. When the polyester film is produced by extruding in multiple layers, the thickness (ratio to all layers) of the preferable inner layer (layer other than the outermost layer) of the obtained polyester film is preferably 50% or more and 95%. % Or less, more preferably 60% or more and 90% or less, and still more preferably 70% or more and 85% or less. Such lamination can be performed by using a feed block mold or a multi-manifold mold.

<Casting> As a method for producing a polyester film, a method is preferred in which, for example, according to the description of [0059] of Japanese Patent Laid-Open No. 2009-269301, a molten material extruded from a mold is extruded onto a casting drum. And cooled and solidified to obtain an unstretched polyester film (original film). In the method for producing a polyester film, the refractive index in the film transport direction (MD direction) of the unstretched polyester film is preferably 1.590 or less, more preferably 1.585 or less, and even more preferably 1.580 or less.

When producing a polyester film, the crystallinity of the unstretched polyester film is preferably 5% or less, more preferably 3% or less, and still more preferably 1% or less. In addition, the crystallinity of the unstretched polyester film mentioned here means the crystallinity of the center part of the film width direction (TD direction). When the crystallinity is adjusted, the temperature of the end of the casting drum can be lowered, or the casting drum can be blown. The crystallinity can be calculated from the density of the film. That is, the density X (g / cm ³ ) of the film, the density Y = 1.335 g / cm ³ when the crystallinity is 0%, and the density Z = 1.501 g / cm ³ when the crystallinity is 100% can be used according to the following The crystallinity (%) is derived by describing the calculation formula. Crystallinity = {Z × (XY)} / {X × (ZY)} × 100 Furthermore, the density is measured in accordance with Japanese Industrial Standards (JIS) K7112.

<Formation of an arbitrary polymer layer> On the unextended polyester film melt-extruded, an arbitrary polymer layer corresponding to the purpose can be formed by coating before or after stretching described later. As an arbitrary polymer layer, the functional layer which a polarizing plate can usually have is mentioned, Among them, it is preferable to form an easy adhesion layer. The easy-adhesive layer can be applied by, for example, the methods described in [0062] to [0070] of WO2012 / 157662.

<Preheating> FIG. 2 schematically shows an example of the configuration of a tenter stretching device used in the horizontal stretching step. As a preheating step before the start of stretching in the transverse stretching step, it is preferable to preheat the unstretched polyester film at a temperature increase rate of 600 ° C./min or less. If the temperature rising rate of the film before the start of stretching in the transverse stretching step is 600 ° C / min or less, the film will be stretched in a state where the molecular chain is sufficiently started to move, and the vertical stress on the shear plane and the yield stress on the shear plane can be suppressed. Excessive increase. From this viewpoint, the temperature rise rate in the preheating step is more preferably 500 ° C / min or less, and even more preferably 400 ° C / min or less.

<Horizontal Extension> In the lateral extension step, a tenter-type extension device (also referred to as "" Tenter "), and stretched laterally in a state where both edges of the unstretched polyester film are clamped by each clamp 13. Furthermore, it is also possible to clamp the unstretched polyester film using a jig from the stage of the preheating step.

The tenter extension device including the jig 13 that moves along a pair of rails provided on both sides of the film conveying path is not particularly limited. A pair of tracks usually uses a pair of circular tracks. The meaning of the jig is the same as that of the clamping member.

The unstretched polyester film was stretched laterally. While the unstretched polyester film is being conveyed along the film conveying road, the film is stretched laterally in a direction (TD) orthogonal to the film conveying direction (MD). That is, lateral extension can be achieved by clamping both ends of the film with a clamp while heating while widening between the clamps.

By performing the lateral extension, the retardation Re in the in-plane direction can be made large. In particular, in order to achieve a polyester film that satisfies the preferable ranges of Re and Re / Rth, it is preferable to extend at least laterally.

The surface temperature at the start of stretching in the lateral stretching step is preferably 80 ° C or higher and 95 ° C or lower, more preferably 82 ° C or higher and 93 ° C or lower, and even more preferably 84 ° C or higher and 92 ° C or lower. If the surface temperature at the beginning of the stretching in the lateral stretching step is 80 ° C. or higher, the alignment and orientation crystallization will not proceed excessively during the stretching stage, and excessive increase in the shear plane vertical stress and shear plane relief stress can be suppressed. In addition, the increase in Rth is suppressed, and the Re / Rth ratio is 0.6 or more, so that rainbow-like unevenness can be suppressed. If the surface temperature at the beginning of the stretching in the lateral stretching step is 95 ° C or lower, the growth of spherulites caused by insufficient alignment is suppressed, and excessive reduction of the vertical stress on the shear plane and the relief stress on the shear plane, and the occurrence of a film can be suppressed. It is cloudy, and Re tends to rise sufficiently.

In the method for producing a polyester film, the surface temperature at the end of stretching in the lateral stretching step is preferably 90 ° C or higher and 105 ° C or lower, more preferably 92 ° C or higher and 102 ° C or lower, and still more preferably 93 ° C or higher and 100 ° C. Below ℃. If the surface temperature at the end of the stretching in the lateral stretching step is 90 ° C. or higher, the orientation and orientation crystallization during the stretching stage will not proceed excessively, and excessive increase in shear plane vertical stress and shear plane relief stress can be suppressed. In addition, the increase in Rth is suppressed, and the Re / Rth ratio is 0.6 or more, so that rainbow-like unevenness can be suppressed. If the surface temperature at the end of the stretching in the lateral stretching step is 105 ° C or lower, the growth of spherulites caused by insufficient alignment is suppressed, and the vertical stress of the shear plane and the excessive reduction of the shear stress in the shear plane can be suppressed, and the film can be prevented from occurring. Re, which is cloudy and affects suppression of rainbow-like unevenness, tends to rise sufficiently.

The surface temperature gradually rises from the beginning to the end of the stretching in the lateral stretching step. Here, the "slow rise" may be a continuous rise or a stepwise rise. The difference in surface temperature between the end of stretching and the start of stretching is preferably 1 ° C or higher, more preferably 3 ° C or higher, and most preferably 5 ° C or higher. If the surface temperature rises slowly from the beginning to the end of the stretching, it will be more difficult to form spherulites, and the excessive alignment can be suppressed. It is easy to have both Re and Re / Rth in their respective better ranges, and the rainbow-like unevenness is not easy to be affected. Recognize.

The lateral extension ratio in the lateral extension step is preferably controlled in a range of 3.3 times or more and 4.8 times or less, more preferably 3.5 times or more and 4.5 times or less, and even more preferably 3.7 times or more and 4.3 times or less. When the lateral extension ratio is 3.3 times or more, excessive reduction in the shearing surface vertical stress and shearing surface undulating stress of the film can be suppressed, and the decrease in Re, which is effective in suppressing rainbow unevenness, is suppressed. If the lateral extension ratio is 4.8 times or less, it is possible to suppress the shear stress on the shear plane and the shear stress in the shear plane from excessively increasing and becoming brittle.

In the lateral stretching step, the surface temperature of the film when the lateral stretching ratio is in a range of 1 to 2 times is preferably 80 ° C or higher and 92 ° C or lower, more preferably 82 ° C or higher and 91 ° C or lower, and even more preferably Above 84 ° C and below 91 ° C. If the surface temperature of the film is in the range of 1 to 2 times in the transverse stretching step in the transverse stretching step, the orientation and orientation crystallization during the stretching stage will not proceed excessively, and the vertical shear plane can be suppressed. The stress and the relief stress on the shear plane are excessively increased. In addition, the increase in Rth is suppressed, and the Re / Rth ratio is 0.6 or more, so that rainbow-like unevenness can be suppressed. If the surface temperature of the film at a lateral extension ratio of 1 to 2 times in the lateral extension step is 92 ° C or lower, the growth of spherulites due to insufficient alignment is suppressed, and vertical stress on the shear plane can be suppressed. And the relief stress on the shear plane was excessively reduced, and Re did not rise sufficiently, and rainbow-like unevenness was recognized.

In the lateral stretching step, the surface temperature of the film when the lateral stretching ratio is in the range of 2 to 3 times is preferably 85 ° C or higher and 97 ° C or lower, more preferably 86 ° C or higher and 97 ° C or lower, and even more preferably Above 87 ° C and below 96 ° C. In the lateral stretching step, if the surface temperature of the film at a lateral stretching ratio in the range of 2 to 3 times is 85 ° C or higher, the orientation and orientation crystallization do not proceed excessively during the stretching stage, and the shear surface can be suppressed. Excessive increase in vertical stress and shear stress in shear plane. In addition, the increase in Rth is suppressed, and the Re / Rth ratio is 0.6 or less, so that rainbow-like unevenness can be suppressed. In the lateral stretching step, if the surface temperature of the film when the lateral stretching ratio is in a range of 2 to 3 times is 97 ° C or lower, the growth of spherulites caused by insufficient alignment is suppressed, and the vertical shear plane can be suppressed. The stress and the relief stress in the shear plane are excessively reduced. In addition, Re, which has an effect on suppressing rainbow-like unevenness, is sufficiently increased, so that rainbow-like unevenness can be suppressed from being recognized.

In the lateral stretching step, the surface temperature of the film when the lateral stretching ratio is in a range of 3 times or more is preferably 90 ° C or higher and 102 ° C or lower, more preferably 92 ° C or higher, 101 ° C or lower, and even more preferably 93 ° C or higher. , Below 100 ° C. In the lateral stretching step, if the surface temperature of the film is 90 ° C or higher when the lateral stretching ratio is in the range of 3 times or more, the orientation and orientation crystallization do not proceed excessively during the stretching stage, and the vertical stress on the shear plane and the The relief stress on the shear plane increases excessively. In addition, the increase in Rth is suppressed, and the Re / Rth ratio is 0.6 or more, so that rainbow-like unevenness can be suppressed. In the lateral stretching step, if the surface temperature of the film when the lateral stretching ratio is in the range of 3 times or more is 102 ° C or lower, the growth of spherulites caused by insufficient alignment is suppressed, and the vertical stress and shear of the shear plane can be suppressed. The tangential relief stress is excessively reduced. In addition, Re is sufficiently raised, and rainbow unevenness can be suppressed from being recognized.

In addition, since the surface temperature gradually rises from the beginning of stretching to the end of stretching, the surface temperature and the lateral stretching ratio of the film at the lateral stretching step in the range of 1 to 2 times in the lateral stretching step. The surface temperature of the film in the range of 2 to 3 times or less and the surface temperature of the film in the range of 3 times or more in the lateral extension ratio do not fall below the surface temperature of the range in the extension in which the lateral extension ratio is small, respectively. That is, the surface temperature of the film when the lateral stretching magnification is in the range of 2 to 3 times or less does not fall below the surface temperature of the film when the lateral stretching magnification is in the range of 1 to 2 times or less, and the lateral stretching magnification is 3 times or more. The surface temperature of the film in the range of 5% does not become the surface temperature of the film or less in the range of the lateral extension magnification of 2 to 3 times or less.

In the lateral stretching step, it is preferable that the temperature increase rate of the surface temperature during stretching is 60 ° C./min or less, more preferably 50 ° C./min or less, and even more preferably 40 ° C./min or less. In the lateral stretching step, if the temperature rise rate of the surface temperature during stretching is 60 ° C./min or less, rapid movement of the molecular chain during stretching can be suppressed, thereby suppressing excessive reduction of vertical stress on the shear plane and excessive stress on the shear plane. small. In addition, Re, which is effective in suppressing rainbow-like unevenness, rises sufficiently, and it is difficult to recognize rainbow-like unevenness.

<Heat Fixation> This embodiment includes a heat fixation step, which is performed by heating the polyester film after the horizontal stretching to the maximum temperature in the horizontal stretching device. Here, the maximum temperature in the heat fixing means the highest point of the film surface temperature reached by the film in the heat fixing region. It can be obtained by actually measuring the film surface temperature in the heat-fixed area using a radiation thermometer. After stretching, a heat treatment called "heat fixation" is performed to promote crystallization. By performing a heat-fixing step of heating at a temperature exceeding the elongation temperature, crystallization can be promoted and the strength of the film can be improved. In heat setting, the polyester film undergoes volume shrinkage for crystallization. As a method of heat fixing, a plurality of slits for sending hot air toward the extension portion can be provided in parallel in the width direction. This is achieved by making the temperature of the gas blown out from the slit higher than the extension. In addition, a heat source (infrared (IR) heater, halogen heater, etc.) may be provided near the extension (part) exit to increase the temperature.

The maximum surface temperature of the polyester film in the heat-setting step is preferably 130 ° C to 230 ° C, more preferably 150 ° C to 210 ° C, and even more preferably 160 ° C to 200 ° C. If the highest reaching surface temperature in the heat-fixing step is 130 ° C or higher, excessive reduction of the vertical stress on the shear plane and the undulating stress of the shear plane can be suppressed. If it is below 230 ° C, the vertical stress and shear on the shear plane can be suppressed. The surface relief stress is excessively increased.

The temperature rising rate of the film from the end of the stretching step to the maximum temperature in the heat fixing step is preferably 1000 ° C./min or less, more preferably 800 ° C./min or less, and even more preferably 700 ° C./min or less.

If the temperature rise rate of the film in the heat-fixing step since the end of the elongation step is 1000 ° C./min or less, the relaxation of molecules before crystallization can be suppressed from proceeding sharply, and the vertical stress on the shear plane and the excessive reduction of the shear stress on the shear plane can be suppressed. It may be small, or Re may not be sufficiently raised, and a rainbow-like unevenness may be recognized.

The time for which the surface temperature exceeds 130 ° C is preferably 180 seconds or less, more preferably 120 seconds or less, and even more preferably 60 seconds or less. If the surface temperature exceeds 130 ° C for 180 seconds or less, the crystallization will not proceed excessively, and excessive increase in the shear plane vertical stress and shear plane relief stress, or excessive increase in Rth, will be recognized as rainbow-like unevenness. Case.

<Heat relaxation> This embodiment preferably includes a heat relaxation step that heats the polyester film after the heat fixing step and reduces at least the film transport direction (MD) and the film transport direction of the polyester film. The length of the orthogonal direction (TD). In addition, the heat-relaxing step is not strictly limited to the state performed after the heat-fixing step, and the heat-fixing step and the heat-releasing step may be performed simultaneously. In the case where the heat fixing step and the heat relaxation step are performed at the same time, the heat fixing step may be performed before the time point when the heating is performed to the maximum temperature in the laterally extending device, and the temperature may be continued at a temperature not exceeding the maximum temperature in the laterally extending device. Heat tempered. It is preferable to perform heat treatment and relaxation (to shrink the film) at the same time after the heat fixing step, and preferably in the TD direction (a direction orthogonal to the film conveying direction: also referred to as a lateral direction), and MD (the film conveying direction: also referred to as For portrait).

It is preferable that the length of the shrinking polyester film in the heat-relief step in a direction orthogonal to the film conveyance direction includes reducing a gap between a pair of rails provided on both sides of the film conveying road, and reducing the polyester in the heat-relief step. The length of the film in the film conveying direction includes the interval between the plurality of clamps that are moved to be narrowed. In the MD direction, before releasing the laterally stretched polyester film from the jig, it is preferable to include a shrinking step in addition to the heat fixing step of heating the laterally stretched polyester film to the maximum temperature in the laterally stretched device. The plurality of jigs moving along a pair of rails provided on both sides of the film conveyance road are spaced from each other. The relaxation by reducing the distance between the clamps can be achieved, for example, by using a pantograph-like chuck in a tenter and reducing the interval between the scales. Alternatively, it can be achieved by using an electromagnet. This is achieved by driving the fixture and reducing the driving speed.

Reducing the length in the film conveying direction of the polyester film in the heat-relieving step can be performed by applying tension to the film conveying direction of the polyester film and reducing the length while conveying it under heating conditions. Under the heating condition, while the polyester film is being transported, the polyester film is applied with a tension below the residual stress of the film, thereby reducing the length of the film during the heating process. By applying tension to the polyester film under heating conditions, the polyester film shrinks during the heating process due to residual stress, so the length in the film transport direction can be reduced. The residual stress of the polyester film can be determined, for example, by measuring the shrinkage force of the film at the time of heating using a thermomechanical analysis device (TMA-60, manufactured by Shimadzu Corporation).

From the viewpoint of further improving the abrasion resistance of the polyester film and suppressing the heat shrinkage ratio, it is preferable that the TD length of the heat-fixed polyester film be reduced, that is, the relaxation rate of the TD is set to 0.1% to 7.0%, more preferably 0.5% to 5.0%, even more preferably 1.0% to 4.0%. With the relaxation rate of TD of 0.1% or more, the thermal shrinkage rate can be reduced. With the relaxation rate of TD of 7% or less, it is difficult to produce slack, wrinkles, damage and other planar faults in the TD during the relaxation process. It is suppressed, which is preferable. In the heat relaxation step, it is preferable to reduce the MD length of the heat-fixed polyester film, that is, the relaxation rate of the MD to be 0.1% to 7%, more preferably 0.5% to 5.0%, and even more It is preferably 1.0% to 4.0%. If the relaxation rate of the MD is 0.1% or more, the heat shrinkage of the MD can be reduced, and it is difficult to cause peeling of the decorative layer or deformation of the film when the decorative film obtained by using the polyester film is pressed. If the relaxation rate of the MD is 7% or less, it is preferable that the relaxation is difficult to occur in the relaxation process and the occurrence of planar faults such as wrinkles and damages is suppressed.

Preferred conditions in the heat-relaxing step for suppressing the heat shrinkage of the polyester film to 3.0% or less include the following conditions: The conveying tension of the polyester film in the heat-relieving step is 10 N / m width to A width of 80 N / m. The temperature of the polyester film during heating is 110 ° C to 190 ° C, and the heat treatment time is 10 seconds to 600 seconds. When the polyester film is cooled after the length of the polyester film is reduced, the polyester film is cooled. The cooling rate when the film surface temperature of the film is in the range of 70 ° C ± 20 ° C is 100 ° C / min to 2000 ° C / min.

The conveying tension of the polyester film in the heat relaxation step is preferably in a range of 10 N / m width to 80 N / m width, more preferably in a range of 15 N / m width to 60 N / m width, and even more preferably 20 N / m width to 40 N / m width. When the transport tension is 10 N / m or more, the occurrence of damage due to friction between the film and the roller during the heat relaxation step is suppressed, and when the transport tension is 80 N / m or less, the polyester can be reduced. The thermal shrinkage of the film suppresses peeling of the decorative layer when the decorative film obtained by using the polyester film is pressed, and deformation of the film after decoration is suppressed.

Regarding the relaxation temperature, as long as the heat-fixing of the stretched polyester film to the maximum temperature in the stretching device can be performed, the temperature can be the same as the heat-fixing (that is, the maximum temperature in the horizontal stretching device can be reached), It can also be lower than the heat fixing temperature. Here, the maximum temperature during thermal relaxation refers to the highest point of the film surface temperature reached by the film in the thermal relaxation region. It can be obtained by actually measuring the film surface temperature in the heat relaxation region using a radiation thermometer. Among these, the film surface temperature of the film during the heat treatment in the heat relaxation step is preferably 110 ° C to 190 ° C, more preferably 120 ° C to 175 ° C, and even more preferably 120 ° C to 160 ° C. When the film surface temperature is 110 ° C. or higher, the thermal shrinkage of the polyester film can be reduced, and peeling of the decorative layer when the decorative film obtained using the polyester film is pressed and deformation of the film after decoration can be suppressed. When the film surface temperature is 190 ° C. or lower, the occurrence of troubles such as the occurrence of wrinkles of the film in the relaxation step is suppressed.

The heat treatment time in the heat relaxation step is preferably 10 seconds to 600 seconds, more preferably 30 seconds to 300 seconds, and even more preferably 60 seconds to 200 seconds. When the heat treatment time is 10 seconds or more, the thermal shrinkage of the polyester film can be reduced, and peeling of the decorative layer when the decorative film obtained by using the polyester film is pressed and deformation of the film after decoration can be suppressed. When the heat treatment time is 600 seconds or less, the occurrence of planar defects such as wrinkles of the film in the heat relaxation step is suppressed.

<Cooling> In this embodiment, it is preferable to include a step of cooling the polyester film before releasing the heat-fixed or heat-relaxed polyester film from the jig. From the viewpoint of easily lowering the temperature of the jig when the polyester film is released from the jig, it is preferable that the polyester film after heat-fixing or thermal relaxation is cooled before being released from the jig. The cooling temperature of the polyester film after heat fixing or heat relaxation is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and particularly preferably 60 ° C. or lower. Specific examples of a method for cooling the heat-fixed polyester film include a method of blowing cold air onto the polyester film. When cooling is performed after the thermal relaxation step, the cooling rate of the film when the film surface temperature of the film is in the range of 70 ° C ± 20 ° C is preferably 100 ° C / min to 2000 ° C / min, and more preferably 300 ° C / min to 1500. ° C / min, more preferably 500 ° C / min to 1000 ° C / min. With a cooling rate of 100 ° C./min or more, the transport distance in the cooling area becomes appropriate, and it is also preferable in terms of device size or cost. In addition, with a cooling rate of 2000 ° C./min or less, occurrence of planar failures such as wrinkles during cooling of the polyester film is suppressed.

Furthermore, as a method of controlling the temperature of heating or cooling the polyester film during preheating, stretching, heat fixing, heat relaxation, and cooling during the production of the polyester film, there may be mentioned: blowing warm air on the polyester film or Cold air, or the polyester film is brought into contact with the surface of a metal plate whose temperature can be controlled, or the polyester film is passed near the metal plate.

By performing the described preheating step, lateral stretching step, heat fixing step, and heat relaxation step, the better heat shrinkage, Re, Rth, and Re / Rth of the polyester film will be easily achieved, so that it can be easily manufactured and can be displayed. A polyester film that reduces rainbow-like unevenness of the polyester film and suppresses curling of decorative films made using the polyester film is produced.

<Release of film from jig> After passing through the steps, release the polyester film from the jig. The surface temperature of the polyester film when the polyester film is detached from the jig is preferably controlled in a range of 40 ° C to 140 ° C. The temperature of the surface of the polyester film when the polyester film is detached from the jig is more preferably 50 ° C or higher and 120 ° C or lower, and even more preferably 60 ° C or higher and 100 ° C or lower.

In the method for manufacturing a polyester film, the thickness of the polyester film after the film formation is completed (after the release step from the jig) is 40 μm or more and 500 μm or less, more preferably 60 μm or more and 400 μm or less, and further It is more preferably 80 μm or more and 300 μm or less. By setting the thickness of the polyester film to the above range, the decorative film having the polyester film as a substrate has sufficient rigidity, and can suppress reduction in punchability and operability caused by excessive rigidity, and dimensional stability. Become better.

<Recycling, cutting, and winding of the film> After releasing from the jig, the film is trimmed, cut, and knurled as necessary, and rolled up for recycling. In the method for producing a polyester film, from the viewpoint of efficiently ensuring the width of the film product and not making the device size too large, it is preferable that the film width after being released from the clamp is 0.8 m to 6 m, and more preferably It is 1 m to 5 m, particularly preferably 1 m to 4 m. The optical film for which accuracy is required is usually formed with a length of less than 3 m, but in this embodiment, it is preferable to form the film with a width as described above. In addition, a film formed with a wide thickness can be cut into two or more and preferably six or less, more preferably two or more and five or less, and even more preferably three or more and four or less. After that, take up.

It is preferable to perform knurl processing (knurling) on both ends after cutting. The winding is preferably performed on a winding core having a diameter of 70 mm or more and 600 mm or less and 1000 m or more and 10,000 m or less. The winding tension per unit cross-sectional area of the film is preferably 30 N / cm ² to 300 N / cm ² , more preferably 50 N / cm ² to 250 N / cm ² , and even more preferably 70 N / cm ² to 200 N / cm ² . In addition, it is also preferable to apply a masking film before winding.

[Hard Coating] The decorative film of the present disclosure has a hard coating on at least one side of a base film including a polyester film. The hard coat layer is preferably used as a protective layer on the outermost surface of the image display device. By placing the hard coat layer on the outermost surface, the abrasion resistance becomes good. From the viewpoint of further improving the abrasion resistance, the hardness of the pencil on the surface of the hard coating layer is preferably H or more, more preferably 3H or more, and even more preferably 5H or more.

<Hard Coating> Hereinafter, the hard coating in the decorative film of this disclosure is demonstrated. The hard coat layer can be formed by any of a wet coating method and a dry coating method (vacuum film formation), and is preferably formed by a wet coating method having excellent productivity. As the hard coat layer, for example, Japanese Patent Laid-Open No. 2013-45045, Japanese Patent Laid-Open No. 2013-43352, Japanese Patent Laid-Open No. 2012-232459, Japanese Patent Laid-Open No. 2012-128157, and Japanese Patent can be used. Japanese Patent Laid-Open No. 2011-131409, Japanese Patent Laid-Open No. 2011-131404, Japanese Patent Laid-Open No. 2011-126162, Japanese Patent Laid-Open No. 2011-75705, Japanese Patent Laid-Open No. 2009-286981, Japanese Patent Japanese Patent Laid-Open No. 2009-263567, Japanese Patent Laid-Open No. 2009-75248, Japanese Patent Laid-Open No. 2007-164206, Japanese Patent Laid-Open No. 2006-96811, Japanese Patent Laid-Open No. 2004-75970, Japanese Patent The hard coatings described in JP 2002-156505, JP 2001-272503, WO12 / 018087, WO12 / 098967, WO12 / 086659, and WO11 / 105594.

(Thickness of Hard Coating Layer) The thickness of the hard coating layer in the decorative film of the present disclosure is preferably 5 μm or more. When the thickness of the hard coat layer is 5 μm or more, a hard coat layer having good scratch resistance can be obtained. From the viewpoint of further improving the scratch resistance, the thickness of the hard coat layer is more preferably 10 μm or more, and even more preferably 15 μm or more. Furthermore, from the viewpoint that the press processing can be easily performed, the thickness of the hard coat layer is preferably 40 μm or less, and more preferably 35 μm or less.

(Constituent material of hard coat layer) The hard coat layer includes at least the structure derived from the following a), the structure derived from the following b), the following c) and the following d). When it is set to 100% by mass, the hard coat layer preferably includes a structure derived from the following a) from 15% by mass to 70% by mass, and a structure derived from the following b) from 25% by mass to 80% by mass. 0.1 to 10% by mass of the following c), 0.1 to 10% by mass of the following d). a) An alicyclic epoxy group and a group containing an ethylenically unsaturated double bond in the molecule, and a compound having a molecular weight of 300 or less b) A group containing three or more ethylenically unsaturated double bonds in the molecule Compound c) a radical polymerization initiator d) a cationic polymerization initiator By providing such a hard coat layer, the decorative film has a high pencil hardness and excellent smoothness, and the change in the appearance of the film after moist heat over time is suppressed.

(Configuration of Hard Coating Layer) The hard coating layer preferably has a configuration formed on at least one surface of the polyester film of the present embodiment described above by a coating method. The hard coating layer is more preferably formed by hardening a hard coating layer-forming composition containing a), b), c), and d), and the total solid content of the hard coating layer-forming composition is 100% by mass. In the case of a hard coating layer, the composition for forming a hard coat layer includes 15% to 70% by mass a), 25% to 80% by mass b), 0.1% to 10% by mass c), and 0.1% to 10% by mass Mass% d).

<Hard-coat layer and composition for hard-coat layer formation> The detail of each component contained in a hard-coat layer and a hard-coat layer formation composition is described below.

-a) A compound having an alicyclic epoxy group and a group containing an ethylenically unsaturated double bond in the molecule and having a molecular weight of 300 or less-When the total solid content of the hard coat layer is 100% by mass Below, the hard-coat layer contains 15 to 70% by mass of a structure derived from the following a). a) A compound having an alicyclic epoxy group and a group containing an ethylenically unsaturated double bond in the molecule and having a molecular weight of 300 or less. In addition, it is preferable that the hard coat layer is formed by hardening a hard coat layer-forming composition including at least a), b), c), and d). The total solid content of the hard coat layer-forming composition is set as In the case of 100% by mass, the composition for forming a hard coat layer contains 15 to 70% by mass of a).

The compound a) contained in the composition for forming a hard coat layer has an alicyclic epoxy group and a group containing an ethylenically unsaturated double bond and has a molecular weight of 300 or less. A) A compound having an alicyclic epoxy group and a group containing an ethylenically unsaturated double bond in the molecule and having a molecular weight of 300 or less is also referred to as "a) component".

Examples of the group containing an ethylenically unsaturated double bond include polymerizable functional groups such as (meth) acrylfluorenyl, vinyl, styryl, and allyl. Among them, (meth) acrylfluorenyl and -C (O) OCH = CH ₂ , particularly preferably (meth) acrylfluorenyl. By having a group containing an ethylenically unsaturated double bond, higher hardness can be maintained, and moist heat resistance can be imparted.

The number of epoxy groups in the molecule and the group containing an ethylenically unsaturated double bond is one. The reason for this is that the molecular weight is reduced by reducing the number of functional groups (epoxy groups and groups containing an ethylenically unsaturated double bond) when the number of each functional group is one compared with the case of two or more. Decreased, pencil hardness further increased.

a) The molecular weight of the component is 300 or less, preferably 210 or less, and more preferably 200 or less. By setting the molecular weight of the component a) to 300 or less, the number of sites other than the epoxy group and the group containing an ethylenically unsaturated double bond is reduced, and pencil hardness can be improved. Moreover, from a viewpoint of suppressing volatilization at the time of forming a hard-coat layer, the molecular weight of a) component is 100 or more, More preferably, it is 150 or more.

The component a) is not limited as long as it has an alicyclic epoxy group and a group containing an ethylenically unsaturated double bond in the molecule, and the molecular weight is 300 or less. It is preferably represented by the following formula (5) The represented compound.

Formula (5)

In formula (5), R represents a monocyclic hydrocarbon or a crosslinked hydrocarbon, L represents a single bond or a divalent linking group, and Q represents a group containing an ethylenically unsaturated double bond.

In the case where R in the formula (5) is a monocyclic hydrocarbon, an alicyclic hydrocarbon is preferable, and among them, an alicyclic group having 4 to 10 carbon atoms is more preferable, and an alicyclic group having 5 carbon atoms is more preferable. Seven alicyclic groups are particularly preferred as alicyclic groups having 6 carbon atoms. Specifically, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl are preferred, and cyclohexyl is particularly preferred. In the case where R in the formula (5) is a crosslinked hydrocarbon, 2-ring system cross-linking (bicyclo ring), 3-ring system cross-linking (tricyclo ring) are preferred, and examples thereof include: Cross-linked hydrocarbons having 5 to 20 carbon atoms include: norbornyl, norbornyl, isobornyl, tricyclodecyl, dicyclopentenyl, dicyclopentyl, tricyclopentenyl, and Tricyclopentyl, adamantyl, adamantyl substituted with lower alkyl, and the like. When L represents a divalent linking group, a divalent aliphatic hydrocarbon group is preferred. As the divalent aliphatic hydrocarbon group, the number of carbons is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1. The divalent aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkylene group, more preferably a linear or branched alkylene group, and even more preferably a linear alkylene group. . Examples of Q include polymerizable functional groups such as (meth) acrylfluorenyl, vinyl, styryl, and allyl. Among these, (meth) acrylfluorenyl and -C (O) OCH = CH are preferred. ₂ , Particularly preferred is (meth) acrylfluorenyl.

The specific compound as component a) is not particularly limited as long as it is a compound having one alicyclic epoxy group and one group containing an ethylenically unsaturated double bond in the molecule and having a molecular weight of 300 or less, and can be used. The compound described in paragraph [0015] of Japanese Patent Laid-Open No. 10-17614, a compound represented by the following formula (1A) or formula (1B), 1,2-epoxy-4-vinylcyclohexane Wait. Among them, a compound represented by the following formula (1A) or formula (1B) is more preferable, and a compound represented by the following formula (1A) having a low molecular weight is more preferable. Furthermore, an isomer of a compound represented by the following formula (1A) is also preferable. In the formula of the following formula (1A), L ₂ represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and from the viewpoint of improving smoothness, still more preferably a carbon number. 1 (that is, a) is an epoxy cyclohexyl methyl (meth) acrylate). By using these compounds, it is possible to achieve high pencil hardness and excellent smoothness at a higher level.

[Chemical 3]

In formula (1A), R ₁ represents a hydrogen atom or a methyl group, and L ₂ represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.

[Chemical 4]

In the formula (1B), R ₁ represents a hydrogen atom or a methyl group, and L ₂ represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.

The divalent aliphatic hydrocarbon group of L ₂ in the formula (1A) and the formula (1B) has a carbon number of 1 to 6, more preferably a carbon number of 1 to 3, and even more preferably a carbon number of 1. The divalent aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkylene group, more preferably a linear or branched alkylene group, and even more preferably a linear alkylene group. .

When the total solid content of the hard coat layer is 100% by mass, a structure derived from a) is contained in an amount of 15% to 70% by mass. That is, when the total solid content of the composition for forming a hard coat layer is 100% by mass, the component a) is contained in an amount of 15% to 70% by mass. When the content of the structure derived from a) or the content of a) is 15% by mass or more with respect to the hard coat layer or the composition for forming a hard coat layer, the effect of improving the smoothness of the surface can be sufficiently obtained. On the other hand, when the structure derived from a) or the content of the a) component is 70% by mass or less with respect to the hard coat layer or the composition for forming a hard coat layer, the surface hardness can be sufficiently increased. When the total solid content of the hard coat layer is 100% by mass, a structure containing 18% to 50% by mass of a) is preferred, and a source containing 22% to 40% by mass is more preferred. Since a) the structure. In the case where the total solid content of the composition for forming a hard coat layer is 100% by mass, it is preferred that the component a) contains 18% to 50% by mass, and more preferably 22% to 40% by mass. a) ingredients.

-b) a compound having three or more groups containing an ethylenically unsaturated double bond in the molecule-when the total solid content of the hard coat layer is 100% by mass, the hard coat layer of the present disclosure contains 25% by mass ~ 80% by mass of the structure derived from the following b). b) A compound having three or more groups containing an ethylenically unsaturated double bond in the molecule. In addition, it is preferable that the hard coat layer is formed by hardening a hard coat layer-forming composition including at least a), b), c), and d). The total solid content of the hard coat layer-forming composition is set as In the case of 100% by mass, the composition for forming a hard coat layer contains 25 to 80% by mass of b).

The compound b) contained in the composition for forming a hard coat layer having three or more groups containing an ethylenically unsaturated double bond will be described. A compound having b) having three or more groups containing an ethylenically unsaturated double bond in its molecule is also referred to as a "b) component". b) The component can exhibit higher hardness by having three or more groups containing an ethylenically unsaturated double bond in the molecule. Examples of the component b) include esters of a polyhydric alcohol and (meth) acrylic acid, vinylbenzene and its derivatives, vinylfluorene, and (meth) acrylamide. Among them, a compound having three or more (meth) acryl fluorenyl groups is preferable from the viewpoint of hardness, and an acrylate compound that forms a hardened product having a high hardness that is widely used in the industry can be cited.

Examples of such compounds include compounds having three or more groups containing an ethylenically unsaturated double bond as an ester of a polyhydric alcohol and (meth) acrylic acid. Examples include: (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide, EO) modified trimethylolpropane tri (meth) acrylate, propylene oxide (PO) modified trimethylolpropane tri (meth) acrylate, EO modified tri (methyl) phosphate Acrylate, trimethylolethane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, (di) pentaerythritol penta (methyl) ) Acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Polyacrylate, caprolactone modified tris (propyleneoxyethyl) isocyanurate, tripentaerythritol triacrylate, tripentaerythritol hexa-triacrylate, 1,2,4-cyclohexane tetrakis (methyl Base) acrylate, pentaglycerol triacrylate, and the like.

Furthermore, a resin (oligomer or prepolymer) having three or more (meth) acrylfluorene groups, a polyfunctional (meth) acrylate having three or more (meth) acrylfluorene groups, and urethane Esters (meth) acrylates are also preferred. Examples of the resin (oligomer or prepolymer) having three or more (meth) acrylfluorene groups include polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, Oligo- or pre-polymers of polyfunctional compounds such as alkyd resins, spiro acetal resins, polybutadiene resins, polythiol polyene resins, and polyols. Specific examples of the polyfunctional (meth) acrylate having three or more (meth) acrylfluorenyl groups include Japanese Patent Laid-Open No. 2007-256844, paragraph 0096, such as dipentaerythritol hexaacrylate (DPHA). Exemplified compounds and the like shown in. Specific examples of the polyfunctional acrylate compound having three or more (meth) acrylfluorene groups include KAYARAD DPHA, DPHA-2C, PET-30, and TMPTA manufactured by Nippon Kayaku Co., Ltd. , TPA-320, TPA-330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, V # 400 manufactured by Osaka Organic Chemical Industry (Stock), V # 36095D Ester of polyhydric alcohols and (meth) acrylic acid. In addition, violet light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, and UV- 6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV-3500BA, UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2750B (manufactured by Japan Synthetic Chemicals Co., Ltd.), UL-503LN (manufactured by Kyoeisha Chemicals Co., Ltd.), Unidic 17 -806, 17-813, V-4030, V-4000BA (manufactured by DIC), EB-1290K, EB-220, EB-5129, EB-1830, EB-4358 (Daicel ) (Manufactured by UCB), Hi-Coap AU-2010, AU-2020 (manufactured by Tokushiki (stock)), Aronix M-1960 (manufactured by East Asia Synthesis (stock) ), Art Resin UN-3320HA, UN-3320HC, UN-3320HS, UN-904, HDP-4T and other trifunctional urethane acrylate compounds, Aronix M-8100 , M-8030, M-9050 (East Asia (Shares), Ltd.), the above KBM-8307 (Daicel Cytec (Daicel-Cytec) (shares) manufactured) trifunctional polyester compound. The component b) may be composed of a single compound, or a plurality of compounds may be used in combination.

When the total solid content of the hard coat layer is 100% by mass, a structure derived from b) is contained in an amount of 25% to 80% by mass. When the total solid content of the composition for forming a hard coat layer is 100% by mass, the component b) is contained in an amount of 25% to 80% by mass. When the content of the structure derived from b) or the content of b) is 25% by mass or more with respect to the hard coat layer or the composition for forming a hard coat layer, sufficient hardness can be obtained. On the other hand, when the structure derived from b) or the content of b) components is 80% by mass or less with respect to the hard coat layer or the composition for forming a hard coat layer, the structure derived from a) or a ) The content of ingredients is reduced, so smoothness is sufficient. When the total solid content of the hard coat layer is 100% by mass, a structure derived from b) containing 40% to 75% by mass is preferred, and a source containing 60% to 75% by mass is more preferred. From b) the structure. When the total solid content of the composition for forming a hard coat layer is 100% by mass, it is preferred that the component b) contains 40% to 75% by mass, and more preferably 60% to 75% by mass. b) composition.

-Other hardenable compounds- The composition for forming a hard coat layer may contain other hardenable compounds (hereinafter, also referred to as "other hardenable compounds") in addition to components a) and b). As other curable compounds, various compounds having a polymerizable group that can be cured (polymerized) by a curing treatment can be used. Examples of the polymerizable group include a polymerizable group capable of performing a polymerization reaction by irradiation with light, an electron beam, or radiation, and a polymerizable group capable of performing a polymerization reaction by heating, and a photopolymerizable group is preferred. The other hardening compound may be a monomer, an oligomer, a prepolymer, or the like.

Specific examples of the polymerizable group include polymerizable unsaturated groups such as (meth) acrylfluorenyl, vinyl, styryl, and allyl, and ring-opening polymerizable polymerizable groups such as epoxy groups. . Among these, a (meth) acrylfluorenyl group is preferable from a viewpoint of hardenability and the like.

As specific examples of other hardenable compounds that can be contained in the composition for forming a hard coat layer, the following compounds can be exemplified. (Meth) acrylic diesters of alkanediols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, and propylene glycol di (meth) acrylate; triethylene glycol bis (methyl) (Meth) acrylic acid esters of polyoxyalkylene glycols such as dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc. Diesters; (meth) acrylic diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; 2,2-bis {4- (propenyloxydiethoxy) phenyl} propane, 2, (Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2-bis {4- (propenyloxypolypropoxy) phenyl} propane; urethane (methyl) Acrylates; polyester (meth) acrylates; isocyanurate acrylates; epoxy (meth) acrylates.

Examples of the urethane (meth) acrylate include a reaction of a hydroxyl-containing compound such as an alcohol, a polyol, and / or a hydroxyl-containing acrylate with an isocyanate, or the use of (meth) acrylic acid as needed. The urethane (meth) acrylate obtained by esterifying the polyurethane compound obtained by the reaction. As specific examples, various commercial products listed in paragraph 0017 of Japanese Patent Laid-Open No. 2007-256844 can be exemplified.

From the viewpoint of reducing hardening shrinkage, the composition for forming a hard coat layer may include an epoxy-based compound having an epoxy group as a polymerizable group as another hardening compound. The epoxy-based compound is preferably a polyfunctional epoxy-based compound containing two or more epoxy groups in one molecule. Specific examples include Japanese Patent Laid-Open No. 2004-264563, Japanese Patent Laid-Open No. 2004-264564, Japanese Patent Laid-Open No. 2005-37737, Japanese Patent Laid-Open No. 2005-37738, and Japanese Patent Laid-Open No. The epoxy compounds described in 2005-140862, Japanese Patent Laid-Open No. 2005-140862, Japanese Patent Laid-Open No. 2005-140863, and Japanese Patent Laid-Open No. 2002-322430. It is also preferable to use a compound having both an epoxy group and an acrylic polymerizable group, such as glycidyl (meth) acrylate.

From the viewpoint of the hardness of the hard coat layer, when the total solid content of the composition for forming a hard coat layer is 100% by mass, it is relative to the total solid content of the composition for forming a hard coat layer. The content of other hardening compounds is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 1% by mass or less, still more preferably 0.01% by mass or less, and particularly preferably not substantially containing other hardening compounds. .

-c) radical polymerization initiator-when the total solid content of the hard coat layer is 100% by mass, the hard coat layer of the present disclosure contains 0.1 to 10% by mass c) radical polymerization initiation Agent. C) A radical polymerization initiator contained in the hard coat layer or the composition for forming a hard coat layer will be described. Hereinafter, c) the radical polymerization initiator is also referred to as "c) component". Polymerization of a compound having an ethylenically unsaturated group can be performed by irradiating ionized radiation or heating in the presence of a photo radical polymerization initiator or a thermal radical polymerization initiator. As the light and thermal polymerization initiator, a commercially available compound can be used, which is described in "Latest UV Hardening Technology" (p.159, Issuer: Takahiro Hiro, Issuer: Technology Information Association (Shares ), Issued in 1991) or Ciba · Specialty · Chemicals (shares) in the product catalog. As component c), specifically, an alkyl phenone-based photopolymerization initiator (Irgacure 651, Irgacure 184, DAROCURE 1173, and Yan Jia Gu ( Irgacure 2959, Irgacure 127, Darocure MBF, Irgacure 907, Irgacure 369, Irgacure 379EG), fluorenyl phosphine oxide system Photopolymerization initiator (Irgacure 819, LUCIRIN TPO), other polymerization initiators (Irgacure 784, Irgacure OXE01, Irgacure) OXE02, Irgacure 754) and so on.

When the total solid content of the hard coat layer or the composition for forming a hard coat layer is 100% by mass, the amount of the component c) is in the range of 0.1% to 10% by mass, preferably 1% by mass to 5 mass%, more preferably 2 mass% to 4 mass%. When the total solid content of the hard coat layer or the composition for forming a hard coat layer is 100% by mass c) When the amount of the component is 0.1% by mass or more, the polymerization proceeds sufficiently and the hard coat pencil can be improved hardness. On the other hand, when the total solid content of the hard coat layer or the composition for forming a hard coat layer is 100% by mass, c) When the amount of the component is 10% by mass or less, UV light reaches the inside of the film, and may Increase the hardness of hard-coated pencils. These c) radical initiators may be used alone or in combination.

-d) Cationic polymerization initiator-When the total solid content of the hard coat layer is 100% by mass, the hard coat layer of the present disclosure includes d) a cationic polymerization initiator. The d) cationic polymerization initiator contained in the hard coat layer or the composition for forming a hard coat layer will be described. Hereinafter, d) the cationic polymerization initiator is also referred to as "d) component". Examples of the component d) include photo-cationic photoinitiators, pigment-based photodecolorants, photochromic agents, and well-known acid generators used in microresists. Compounds and mixtures thereof. For example, an onium compound, an organic halogen compound, and a difluorene compound are mentioned. Specific examples of the organic halogen compound and the difluorene compound include the same compounds as described above for the compound that generates a radical.

Examples of the onium compounds include diazonium salts, ammonium salts, imine salts, sulfonium salts, sulfonium salts, sulfonium salts, sulfonium salts, selenium salts, and the like, and for example, paragraph number [0058 of Japanese Patent Laid-Open No. 2002-29162] can be cited. ] To the compounds described in paragraph number [0059].

In the present disclosure, as the cationic polymerization initiator that can be particularly suitably used, an onium salt is mentioned. In terms of the photosensitivity of photopolymerization initiation and the stability of the raw materials of the compound, diazonium salts and sulfonium salts are preferred. Among sulfonium salts and sulfonium salts, sulfonium salts are most preferred from the viewpoint of light resistance.

Specific examples of the onium salt that can be suitably used in the present disclosure include, for example, the sulfonated sulfonium salts described in paragraph No. [0035] of Japanese Patent Laid-Open No. 9-268205 and Japanese Patent Specialties. A diarylsulfonium salt or a triarylsulfonium salt described in paragraph numbers [0010] to paragraph number [0011] of Japanese Patent Publication No. 2000-71366, and a paragraph number [0017] of Japanese Patent Laid-Open No. 2001-288205 The sulfonium salts of the thiobenzoic acid S-phenyl esters described, the onium salts described in paragraphs [0030] to [0033] of Japanese Patent Laid-Open No. 2001-133696, and the like.

As another example, the organic metal / organic halide described in Japanese Patent Application Laid-Open No. 2002-29162, paragraph numbers [0059] to paragraph number [0062], and light having an o-nitrobenzyl type protecting group can be mentioned. Compounds such as acid generators and compounds (such as iminosulfonates) that generate sulfonic acids by photodecomposition.

As a specific compound of a sulfonium-based cationic polymerization initiator, B2380 (manufactured by Tokyo Chemical Industry), BBI-102 (manufactured by Green Chemical), WPI-113 (manufactured by Wako Pure Chemical Industries), WPI-124 (wakako Pure Chemical Pharmaceutical Industry Manufacturing), WPI-169 (Wako Pure Chemical Industries Manufacturing), WPI-170 (Wako Pure Chemical Industries Manufacturing), DTBPI-PFBS (Toyo Synthetic Chemical Manufacturing).

Furthermore, as a preferable example of a sulfonium-type cationic polymerization initiator, the following compounds FK-1 and FK-2 are mentioned.

Photocationic polymerization initiator (phosphonium salt compound) FK-1 [Chem. 5]

Photocationic polymerization initiator (phosphonium salt compound) FK-2 [Chem. 6]

As component d), only one kind may be used, or two or more kinds may be used in combination. When the total solid content of the hard coat layer or the composition for forming a hard coat layer is 100% by mass, the component d) is added in the range of 0.1% to 10% by mass, preferably 0.5% by mass. It is added in a proportion of -3.0% by mass. The addition amount in the above range is preferable in terms of stability, polymerization reactivity, and the like of the curable composition.

-Other components of the hard coat layer- The hard coat layer may contain other components in addition to components a) to d), which are preferable components.

-e) Inorganic particles that are reactive with epoxy groups or groups containing ethylenically unsaturated double bonds-It is preferred to add e) and epoxy groups or to Reactive inorganic particles having a group of ethylenically unsaturated double bonds. Hereinafter, e) inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond are also referred to as "e) component". By adding inorganic particles, the amount of hardening shrinkage of the hard coat layer (hardened layer) can be reduced, so smoothness can be improved. Furthermore, pencil hardness can be improved by using inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond. Examples of the inorganic particles include silicon dioxide particles, titanium dioxide particles, zirconia particles, and alumina particles. Among them, the inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond are preferably silica particles.

In general, inorganic particles have low affinity with organic components such as polyfunctional vinyl monomers. Therefore, if they are mixed only, aggregates may be formed, or hardened hard coatings may be easily cracked. Therefore, in the component e), in order to increase the affinity between the inorganic particles and the organic component, it is preferable to treat the surface of the inorganic particles with a surface modifier containing an organic segment. The surface modifier is preferably a surface modifier having a functional group capable of forming a bond with the inorganic particle or adsorbable to the inorganic particle, and a functional group having an affinity for an organic component in the same molecule. As the surface modifier having a functional group capable of bonding or adsorbing to inorganic particles, a metal alkoxide surface modifier such as silane, aluminum, titanium, zirconium, or the like, or a phosphate group, a sulfuric acid group, a sulfonic acid group, Surface modifiers for anionic groups such as carboxylic acid groups. Furthermore, the functional group having an affinity with the organic component may be only a functional group that is compatible only with the hydrophobicity and the organic component, but is preferably a functional group capable of chemically bonding with the organic component, and particularly preferably contains ethylene. A group of unsaturated double bonds or a ring-opening polymerizable group. In the present disclosure, a preferable surface modifier of the inorganic particles is a metal alkoxide, or a curable resin having an anionic group and a group containing an ethylenically unsaturated double bond or a ring-opening polymerizable group in the same molecule. By chemically bonding with an organic component, the crosslinking density of the hard coat layer increases, and pencil hardness can be increased.

Representative examples of these surface modifiers include the following unsaturated double bond-containing coupling agents, organic curable resins containing a phosphoric acid group, organic curable resins containing a sulfuric acid group, and organic curable resins containing a carboxylic acid group. Wait. S-1 H ₂ C = C (X) COOC ₃ H ₆ Si (OCH ₃ ) ₃ S-2 H ₂ C = C (X) COOC ₂ H ₄ OTi (OC ₂ H ₅ ) ₃ S-3 H ₂ C = C (X) COOC ₂ H ₄ OCOC ₅ H ₁₀ OPO (OH) ₂ S-4 (H ₂ C = C (X) COOC ₂ H ₄ OCOC ₅ H ₁₀ O) ₂ POOH S-5 H ₂ C = C (X) COOC ₂ H ₄ OSO ₃ H S-6 H ₂ C = C (X) COO (C ₅ H ₁₀ COO) ₂ H S-7 H ₂ C = C (X) COOC ₅ H ₁₀ COOH S-8 CH ₂ CH (O) CH ₂ OC ₃ H ₆ Si (OCH ₃ ) ₃ (X represents a hydrogen atom or CH ₃ )

The surface modification of these inorganic particles is preferably achieved in a solution. The method may be as follows: when the inorganic particles are mechanically finely dispersed, a surface modifier is present together; or after the inorganic particles are finely dispersed, a surface modifier is added and stirred; or further, the inorganic particles are surface-modified before being finely dispersed. (If necessary, after heating, drying, or heating, or changing the pH), fine dispersion is performed thereafter. As the solution for dissolving the surface modifier, an organic solvent having a large polarity is preferred. Specific examples include known solvents such as alcohols, ketones, and esters.

Considering the balance between the hardness and brittleness of the coating film, when the total solid content of the hard coat layer or the composition for forming a hard coat layer is 100% by mass, the amount of the component e) is preferably 5% by mass to 40 mass%, more preferably 10 mass% to 30 mass%. The size (average primary particle diameter) of the inorganic particles is preferably 10 nm to 100 nm, and more preferably 10 nm to 60 nm. The average particle diameter of the particles can be determined from an electron microscope photograph. When the particle diameter of the inorganic particles is greater than or equal to the lower limit, the effect of improving the hardness can be obtained, and if it is equal to or less than the upper limit, the increase in haze can be suppressed. The shape of the inorganic particles may be spherical or non-spherical, but from the viewpoint of imparting hardness, a non-spherical shape in which two to ten inorganic particles are connected is preferable. It is estimated that hardness is improved by forming a strong particle network structure by using inorganic particles in which several inorganic particles are connected in a chain shape. Specific examples of the inorganic particles include: ELECOM V-8802 (spherical silicon dioxide particles with an average primary particle diameter of 12 nm manufactured by Niwa Corporation), and ELECOM V- 8803 (Nano-shaped silicon dioxide particles manufactured by Niwa Co., Ltd.), MiBK-SD (Spherical silicon dioxide particles with an average primary particle size of 10 nm to 20 nm manufactured by Nissan Chemical Industries, Ltd.), MEK-AC-2140Z (Spherical silica particles with an average primary particle size of 10 nm to 20 nm manufactured by Nissan Chemical Industry Co., Ltd.), MEK-AC-4130 (average primary particle size of 40 nm to 50 manufactured by Nissan Chemical Industry Co., Ltd.) nm spherical silica particles), MiBK-SD-L (spherical silica particles with an average primary particle size of 40 nm to 50 nm manufactured by Nissan Chemical Industries, Ltd.), MEK-AC-5140Z (Nissan Chemical Industry (Stock) manufactured spherical silica particles with an average primary particle diameter of 70 nm to 100 nm). Among these, from the viewpoint of imparting surface hardness, ELECOM V-8803 is preferred.

-f) polyester urethane-In the hard coat layer or the composition for forming a hard coat layer in the present disclosure, from the viewpoint of improving brittleness, it is preferable to contain f) polyester urethane . Hereinafter, f) polyester urethane is also referred to as "f) component". The polyester urethane refers to a polymer containing an ester bond and a urethane bond (-O-CO-NH-) in one molecule. f) The polyester urethane is preferably a polyester urethane having a tensile strength of 25 MPa or more and a tensile elongation of 200% or more. A polyester urethane having a tensile strength of 25 MPa or more and a tensile elongation of 200% or more is thought to contribute to the increase in hardness of the hard coat layer and impart appropriate softness. This is expected to contribute to the increase in hardness and brittleness of the hard coating layer. In addition, if the polyester urethane content is 100 parts by mass or more with respect to 100 parts by mass of the total solid content of the hard coat layer or the composition for forming the hard coat layer, it is possible to sufficiently obtain polyester by adding polyester When the said effect of a urethane is 10 mass parts or less, the hardness of a hardened layer can be maintained. Therefore, the polyester urethane content is set to the range of 1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the hard coat layer or the composition for forming the hard coat layer. From the viewpoint of improving the brittleness and suppressing the decrease of transparency, it is more preferably 2 parts by mass or more, and from the viewpoint of maintaining the hardness of the hard coat layer, it is more preferably 8 parts by mass or less.

When a polyester urethane exhibiting the above-mentioned tensile strength and tensile elongation is used as the polyester urethane, it contributes to achieving high hardness by imparting moderate softness to the hard coat layer. Both increase and decrease brittleness. The tensile strength is more preferably 40 MPa or more, and even more preferably 50 MPa or more. From the viewpoint of compatibility and stability in the composition for forming a hard coat layer, the tensile strength is preferably 70 MPa or less. On the other hand, the tensile elongation is preferably 450% or more, and more preferably 600% or more. From the viewpoint of ensuring pencil hardness, which is one of the indicators of film hardness, the tensile elongation is preferably 1,000% or less. A method for measuring pencil hardness will be described later with reference to Examples. The tensile strength and tensile elongation of the polyester urethane were measured according to JIS K 6251 using a tensile strength tester.

The polyester urethane can be obtained by polymerization of a monomer component including at least a diol, a dicarboxylic acid, and a diisocyanate. As the three types of monomers described above, a polyester amino group having a hydroxyl group (-OH), a carboxyl group (-COOH), and an isocyanate group (-NCO) at both ends of a hydrocarbon group having an unbranched structure is preferred. Acid ester. The hydrocarbon group having an unbranched structure is preferably an alkylene group, an alkenyl group, an alkynyl group, an arylene group, or a combination thereof. The alkylene, alkenyl and alkynyl groups preferably have a linear structure. When the hydrocarbon group is an alkylene group, an alkylene group, or an alkylene group, the number of carbon atoms is preferably 1 to 8, more preferably 2 to 6, and even more preferably 2 to 4. The arylene group may have an alkyl group having 1 to 8 carbon atoms as a substituent. The arylene group is preferably a phenylene group or a naphthyl group, more preferably a phenylene group, and even more preferably a p-phenylene group. The hydrocarbon group is particularly preferably the alkylene group, the alkylene group, or a combination thereof.

The diol used as a monomer of the polyester urethane is preferably ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, or 1,6-hexanediol. , 1,4-cyclohexanedimethanol and 1,5-pentanediol. As the dicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, oxalic acid, and Malonate. The diisocyanate is preferably ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-phenylene diisocyanate, and toluene diisocyanate p. , p'-diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate.

From the viewpoint of affinity with inorganic particles, the number average molecular weight (Mn) of the polyester urethane is preferably 5,000 or more, and more preferably 10,000 or more. From the viewpoint of compatibility with the hardening compound, In other words, it is preferably 50,000 or less.

In addition, in one aspect, the polyester urethane may have a reactive group. The reactive group is preferably a polymerizable unsaturated group. Specific examples are as described in the previous description of the functional groups that the inorganic particles may have.

As the polyester urethane described above, a polyester urethane synthesized by a known method may be used, or a commercially available product may be used. Examples of commercially available products include Vylon (registered trademark) series (trade name): manufactured by Toyobo Co., Ltd., and Vylon UR-2300, Vylon UR- 3200, Vylon UR-3210, Vylon UR-3260, Vylon UR-5537, 300 Vylon UR-8300, Vylon UR-8700, etc.

-g) Antifouling agent-When the g) antifouling agent is contained in the hard coat layer or the composition for forming a hard coat layer in the present disclosure, the adhesion of fingerprints and stains is reduced, and the erasure of attached stains is changed. To be simple and better. It is also preferable from the viewpoint of improving the abrasion resistance by improving the smoothness of the surface. Hereinafter, g) antifouling agent is also called "g) component. The hard coating of the present disclosure is preferably: g) the antifouling agent contains a fluorine-containing compound, and the contained fluorine-containing compound has a perfluoropolyether group and a polymerizable unsaturated group, and has a plurality of polymerizable compounds in one molecule. Saturated group. The g) antifouling agent that can be used in the present disclosure will be described.

[Fluorine-containing compound having a polymerizable unsaturated group] For g) the antifouling agent contains a fluorine-containing compound, and the contained fluorine-containing compound has a perfluoropolyether group and a polymerizable unsaturated group and has a plurality of molecules in one molecule. A case of a polymerizable unsaturated compound (hereinafter, also referred to as a "fluorine-containing antifouling agent") will be described. The fluorine-containing antifouling agent is preferably a fluorine-based compound containing a structure represented by the following formula (F). Formula (F): (Rf)-[(W)-(R _A ) _n ] _{m In the} formula, Rf represents a (per) fluoroalkyl or (per) fluoropolyether group, W represents a linking group, and R _A represents polymerization Sexual unsaturation. n represents an integer of 1 to 3. m represents an integer of 1 to 3.

The fluorine-containing antifouling agent is considered to have the following effects (1) to (3) by having a polymerizable unsaturated group. (1) Since solubility in an organic solvent and compatibility with a compound having an unsaturated double bond and the like are improved, it is considered that the antifouling agent does not form aggregates and can be uniformly locally present on the surface. In addition, defects caused by aggregates can be prevented. (2) Even if the fluorine-containing antifouling agent exists locally on the surface, the fluorine-containing antifouling agents can form covalent bonds with each other or with compounds having unsaturated double bonds through photopolymerization, so it can prevent abrasion. Peeling of antifouling agents and deterioration of antifouling properties. (3) It is possible to prevent loss of antifouling property and deterioration of appearance due to precipitation of antifouling agent.

In formula (F), R _A represents a polymerizable unsaturated group. The polymerizable unsaturated group is not particularly limited as long as it is a group capable of inducing a radical polymerization reaction by irradiating an active energy ray such as ultraviolet rays or electron beams, and examples thereof include (meth) acrylfluorenyl groups and (meth) acrylfluorene As the alkoxy group, vinyl group, allyl group, etc., a (meth) acrylfluorenyl group, a (meth) acrylfluorenyloxy group, and any of these groups in which any hydrogen atom is substituted with a fluorine atom can be preferably used. base. As a specific example of a polymerizable unsaturated group, the group which has a structure shown below is preferable.

[Chemical 7]

In the formula (F), Rf represents a (per) fluoroalkyl group or a (per) fluoropolyether group. Here, the (per) fluoroalkyl group means at least one of a fluoroalkyl group and a perfluoroalkyl group, and the (per) fluoropolyether group means at least one of a fluoropolyether group and a perfluoropolyether group. From the viewpoint of antifouling properties, it is preferred that the fluorine content in Rf is high.

The (per) fluoroalkyl group is preferably a group having 1 to 20 carbon atoms, and more preferably a group having 1 to 10 carbon atoms. The (per) fluoroalkyl group may be a straight chain (for example, -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, -CH ₂ (CF ₂ ) ₈ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₄ H Etc.), can also be branched structures (such as CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc. ), Can also be alicyclic structure (preferably 5-membered ring or 6-membered ring, such as perfluorocyclohexyl, perfluorocyclopentyl or these substituted alkyl groups, etc.).

The (per) fluoropolyether group refers to a case where the (per) fluoroalkyl group has an ether bond, and may be a monovalent group or a divalent or higher group. Examples of the fluoropolyether group include -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , -CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, a fluorocycloalkyl group having 4 to 20 carbon atoms having 4 or more fluorine atoms, and the like. Examples of the perfluoropolyether group include-(CF ₂ O) _p- (CF ₂ CF ₂ O) _q -,-[CF (CF ₃ ) CF ₂ O] _p- [CF ₂ (CF ₃ )]-,-(CF ₂ CF ₂ CF ₂ O) _p -,-(CF ₂ CF ₂ O) _p -and so on. The total of p and q is preferably 1 to 83, more preferably 1 to 43, and most preferably 5 to 23. From the viewpoint of excellent antifouling properties, the fluorinated antifouling agent is particularly preferably one having a perfluoropolyether group represented by-(CF ₂ O) _p- (CF ₂ CF ₂ O) _q- . The p and q each independently represent an integer of 0 to 20. Here, p + q is an integer of 1 or more.

From the viewpoint that the effects shown in (1) to (3) can be more significantly obtained, the fluorine-containing antifouling agent preferably has a perfluoropolyether group and a plurality of polymerizable unsaturated groups in one molecule. base.

In formula (F), W represents a linking group. Examples of W include an alkylene group, an alkylene group, a heteroalkylene group, or a combination thereof. These linking groups may further have a functional group such as an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamido group, or the like, or a combination thereof. As W, an ethylene group is preferred, and an ethylene group bonded to a carbonylimino group is more preferred.

From the viewpoint that the effects shown in the above (1) to (3) can be more significantly obtained, in the formula (F), the product of n and m (n × m) is preferably 2 or more, more preferably 4 the above.

In the formula (F), when n and m are both 1, the following formulas (F-1) to (F-3) can be cited as specific examples of the following preferable aspects.

Formula (F-1): Rf ² (CF ₂ CF ₂ ) _p R ' ² CH ₂ CH ₂ R ² OCOCR ¹ = CH ₂

In the formula (F-1), Rf ² represents any of a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms, R ¹ represents a hydrogen atom or a methyl group, R ² represents a single bond or an alkylene group, and R ' ² Represents a single bond or a divalent linking group, p is an integer representing a degree of polymerization, and the degree of polymerization p is k (k is an integer of 3 or more) or more.

When R ′ ² represents a divalent linking group, examples of the divalent linking group include the same linking groups as W.

Examples of the telomer-type acrylate containing a fluorine atom in the formula (F-1) include a partially fluorinated or fully fluorinated alkyl ester derivative of (meth) acrylic acid.

Specific examples of the compound represented by the formula (F-1) are shown below, but are not limited to these compounds.

[Chemical 8]

When the compound represented by the formula (F-1) is synthesized using short-chain polymerization, the compound Rf ^{2 of the} formula (F-1) may be included depending on the conditions of the short-chain polymerization and the separation conditions of the reaction mixture. (CF ₂ CF ₂ ) _p R ′ ² CH ₂ CH ₂ R ² O— p is a plurality of fluorine-containing (meth) acrylates each having k, k + 1, k + 2, etc.

Formula (F-2): F (CF ₂ ) _q -CH ₂ -CHX-CH ₂ Y In formula (F-2), q is an integer of 1 to 20, and X and Y are each independently (meth) propylene. Either a fluorenyloxy group or a hydroxyl group, and at least one of which is a (meth) acrylic fluorenyloxy group.

The fluorine-containing (meth) acrylate represented by the formula (F-2) contains a fluoroalkyl group having 1 to 20 carbon atoms having a trifluoromethyl group (CF _3- ) at the terminal, and the fluorine-containing (methyl) group Even with a small amount of acrylate, trifluoromethyl is effectively aligned on the surface.

In terms of antifouling properties and ease of production, q is preferably 6 to 20, and more preferably 8 to 10. A fluorine-containing (meth) acrylate having a fluoroalkyl group having 8 to 10 carbon atoms exhibits superior water repellency × oil repellency compared to a fluorine-containing (meth) acrylate having a fluoroalkyl group having another chain length. Therefore, it is excellent in stain resistance.

Specific examples of the fluorine-containing (meth) acrylate represented by the formula (F-2) include 1- (meth) acrylfluorenyloxy-2-hydroxy-4,4,5,5, 6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-Docosafluorotridecane, 2- (meth) acrylic acid Oxyoxy-1-hydroxy-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13- Twenty-one tridecane and 1,2-bis (meth) propenyloxy 4,4,5,5,6,6,7,7,8,9,9,10,10, 11,11,12,12,13,13,13-twelve-fluorotridecane and the like. In the present disclosure, 1-propenyloxy-2-hydroxy-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11, 11,12,12,13,13,13-Ticosfluorotridecane.

Formula (F-3): F (CF ₂ ) _r O (CF ₂ CF ₂ O) _s CF ₂ CH ₂ OCOCR ³ = CH _{2 In} formula (F-3), R ³ is a hydrogen atom or a methyl group, and s is An integer of 1 to 20, and r represents an integer of 1 to 4.

The fluorine atom-containing monofunctional (meth) acrylate represented by the formula (F-3) can be obtained by combining a fluorine atom-containing alcohol compound represented by the following formula (FG-3) with (methyl ) Acrylic halide reaction is obtained.

Formula (FG-3): F (CF ₂ ) _r O (CF ₂ CF ₂ O) _s CF ₂ CH ₂ OH In formula (FG-3), s is an integer from 1 to 20, and r is an integer from 1 to 4. .

Specific examples of the fluorine atom-containing alcohol compound represented by the formula (FG-3) include 1H, 1H-perfluoro-3,6-dioxaheptane-1-ol, 1H, 1H- Perfluoro-3,6-dioxaoctane-1-ol, 1H, 1H-perfluoro-3,6-dioxadecane-1-ol, 1H, 1H-perfluoro-3,6,9 -Trioxadecane-1-ol, 1H, 1H-perfluoro-3,6,9-trioxaundecane-1-ol, 1H, 1H-perfluoro-3,6,9-trioxane Heptadecane-1-ol, 1H, 1H-perfluoro-3,6,9,12-tetraoxatridecane-1-ol, 1H, 1H-perfluoro-3,6,9,12- Tetraoxatetradecan-1-ol, 1H, 1H-perfluoro-3,6,9,12-tetraoxahexadecane-1-ol, 1H, 1H-perfluoro-3,6,9, 12,15-pentaoxahexadec-1-ol, 1H, 1H-perfluoro-3,6,9,12,15-pentaoxahexadecane-1-ol, 1H, 1H-perfluoro- 3,6,9,12,15-pentahexadecane-1-ol, 1H, 1H-perfluoro-3,6,9,12,15,18-hexaoxaecosane-1-ol , 1H, 1H-perfluoro-3,6,9,12,15,18-hexaoxadocosa-1-ol, 1H, 1H-perfluoro-3,6,9,12,15,18 , 21-heptaoxane-1-ol, 1H, 1H-perfluoro-3,6,9,12,15,18,21-heptaoxapentadecan-1-ol, etc. These compounds are available on the market. As specific examples, for example, 1H, 1H-perfluoro-3,6-dioxaheptane-1-ol (trade name "C5GOL", Exfluor (Exfluor ), 1H, 1H-perfluoro-3,6,9-trioxadecane-1-ol (trade name "C7GOL", manufactured by Exfluor), 1H, 1H-full Fluoro-3,6-dioxadecane-1-ol (trade name "C8GOL", manufactured by Exfluor), 1H, 1H-perfluoro-3,6,9-trioxade Trialk-1-ol (trade name "C10GOL", manufactured by Exfluor), 1H, 1H-perfluoro-3,6,9,12-tetraoxahexadec-1-ol ( Trade name "C12GOL", manufactured by Exfluor Corporation). In the present disclosure, 1H, 1H-perfluoro-3,6,9,12-tetraoxatridecane-1-ol is preferably used.

Examples of the (meth) acrylic fluorene halide that reacts with a fluorine atom-containing alcohol compound represented by the formula (FG-3) include (meth) acrylic fluorene, (meth) acrylic fluorene, and ( (Meth) acrylic acid bromide, (meth) acrylic acid iodine. From the viewpoint of easy availability and the like, (meth) acrylic acid chloride is preferred.

Preferred specific examples of the compound represented by the formula (F-3) are shown below, but are not limited to these specific examples. Further, a preferred specific example represented by the formula (F-3) is also described in Japanese Patent Laid-Open No. 2007-264221.

(B-1): F ₉ C ₄ OC ₂ F ₄ OC ₂ F ₄ OCF ₂ CH ₂ OCOCH = CH ₂ (b-2): F ₉ C ₄ OC ₂ F ₄ OC ₂ F ₄ OCF ₂ CH ₂ OCOC ( CH ₃ ) = CH ₂

Furthermore, the compound represented by the following formula (F-3A) can be preferably used separately from the compound represented by the formula (F-3).

The compound is of formula (F-3A): Rf ³ -[(O) _c (O = C) _b (CX ⁴ X ⁵ ) _a -CX ³ = CX ¹ X ² ] (wherein X ¹ and X ² Each independently represents H or F, X ³ represents H, F, CH ₃ or CF ₃ , X ⁴ and X ⁵ each independently represent H, F or CH ₃ , a, b and c each independently represent 0 or 1, Rf ³ represents a fluorine-containing alkyl group containing an ether bond having 18 to 200 carbon atoms, and has 6 or more of the Rf ³ group. Formula (FG-3A):-(CX ⁶ ₂ CF ₂ CF ₂ O)- A fluorine-containing unsaturated compound having a repeating unit represented by (wherein X ⁶ is F or H).

Examples of the fluorine-containing polyether compound represented by the formula (F-3A) include: (c-1) Rf ³ -[(O) (O = C) _b -CX ³ = CX ¹ X ² ] ( c-2) Rf ³ -[(O) (O = C) -CX ³ = CX ¹ X ² ] (c-3) Rf ³ -[(O) _c (O = C) -CF = CH ₂ ] etc. As the polymerizable unsaturated group of the fluorine-containing polyether compound, a group having the following structure is preferred. The definitions of the symbols in (c-1) to (c-3) have the same meanings as in the formula (FG-3A).

[Chemical 9]

In addition, the fluorinated polyether compound represented by the formula (F-3A) may have a plurality of polymerizable unsaturated groups, and a structure such as the structure shown below is preferably exemplified.

[Chemical 10]

In the present disclosure, a compound having a structure of -O (C = O) CF = CH ₂ has a particularly high polymerization (hardening) reactivity, and a cured product can be obtained efficiently, which is preferable in this respect.

In the fluorinated polyether compound represented by the formula (F-3A), as for the Rf ³ group, it is important that the fluorinated polyether chain of the formula (FG-3A) includes 6 in Rf ³ as a repeating unit. As described above, antifouling properties can be provided by this. In more detail, a mixture of 6 or more compounds containing a repeating unit containing a fluorinated polyether chain may be used. However, when used in the form of a mixture, it is preferable to use the following mixture: In the distribution of less than 6 fluorine-containing unsaturated compounds and fluorine-containing unsaturated compounds having 6 or more repeating units, the presence ratio of the fluorine-containing unsaturated compounds having 6 or more repeating units in the polyether chain is highest. The repeating unit of the fluorine-containing polyether chain of the formula (FG-3A) is preferably 6 or more, more preferably 10 or more, still more preferably 18 or more, and particularly preferably 20 or more. Thereby, not only the water repellency can be improved, but also the antifouling property can be improved, and in particular, the removability of stains containing an oil component can be improved. In addition, breathability can be provided more effectively. In addition, the fluorine-containing polyether chain may be located at the terminal of the Rf ³ group, or may be present in the middle of the chain.

Specifically, the Rf ³ group is preferably the formula (c-4): R ^4- (CX ⁶ ₂ CF ₂ CF ₂ O) _t- (R ⁵ ) _e- (where X ⁶ and formula (FG-3A ) Are the same, R ⁴ represents a hydrogen atom, a halogen atom, or at least one selected from the group consisting of an alkyl group, a fluorine-containing alkyl group, an alkyl group containing an ether bond, and a fluorine-containing alkyl group containing an ether bond, and R ⁵ represents a divalent or more organic Base, t represents an integer from 6 to 66, and e represents a structure of 0 or 1). That is, the Rf ³ group is a fluorine-containing organic group which is bonded to a reactive carbon-carbon double bond via an organic group R ⁵ having a valence of two or more, and further has R ⁴ at the terminal. R ⁵ may be any organic group as long as it is an organic group capable of bonding a fluorinated polyether chain of the formula (FG-3A) to a reactive carbon-carbon double bond. For example, it may be selected from an alkylene group, a fluorine-containing alkylene group, an alkylene group containing an ether bond, and a fluorine-containing alkylene group containing an ether bond. Among these, in terms of transparency and low refractive index, a fluorine-containing alkylene group and a fluorine-containing alkylene group including an ether bond are preferred.

As specific examples of the fluorinated polyether compound represented by the formula (F-3A), the compounds and the like listed in the pamphlet of WO2003 / 022906 can be preferably used. In this disclosure, CH ₂ = CF-COO-CH ₂ CF ₂ CF _2- (OCF ₂ CF ₂ CF ₂ ) ₇ -OC ₃ F ₇ can be particularly preferably used.

In the formula (F), regarding the case where n and m are not both 1, the formula (F-4) and the formula (F-5) can be listed as the following preferred aspects.

Formula (F-4): (Rf ¹ )-[(W)-(R _A ) _n ] _m (In formula (F-4), Rf ¹ represents a (per) fluoroalkyl group or a (per) fluoropolyether group) , W represents a linking group, and R _A represents a functional group having an unsaturated double bond. N represents an integer of 1 to 3, m represents an integer of 1 to 3, and n is not 1 when m is different. From the viewpoint of excellent water repellency (continuous antifouling durability), n is preferably 2 to 3, m is 1 to 3, more preferably n is 2 to 3, and m is 2 to 3, and most preferably n is 3 and m is 2 to 3.

Rf ¹ may use a monovalent to trivalent radical. In the case where Rf ¹ is monovalent, the terminal groups are preferably (C _n F _{2n + 1} )-, (C _n F _{2n + 1} O)-, (XC _n F _2n O)-, (XC _n F _{2n + 1} )-(wherein X is hydrogen, chlorine or bromine, and n is an integer from 1 to 10). Specifically, CF ₃ O (C ₂ F ₄ O) _p CF _2- , C ₃ F ₇ O (CF ₂ CF ₂ CF ₂ O) _p CF ₂ CF _2- , C ₃ F ₇ O can be preferably used. (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ )-, F (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ )-, and the like.

Here, the average value of p is 0-50. It is preferably 3 to 30, more preferably 3 to 20, and most preferably 4 to 15.

In the case where Rf ¹ is divalent,-(CF ₂ O) _q (C ₂ F ₄ O) _r CF ₂ -,-(CF ₂ ) ₃ O (C ₄ F ₈ O) _r ( CF ₂ ) _3- , -CF ₂ O (C ₂ F ₄ O) _r CF _2- , -C ₂ F ₄ O (C ₃ F ₆ O) _r C ₂ F _4- , -CF (CF ₃ ) (OCF ₂ CF (CF ₃ )) _s OC _t F _2t O (CF (CF ₃ ) CF ₂ O) _r CF (CF ₃ )-and so on.

Here, the average value of q, r, and s in the formula is 0 to 50. It is preferably 3 to 30, more preferably 3 to 20, and most preferably 4 to 15. t is an integer from 2 to 6. Preferred specific examples or synthetic methods of the compound represented by the formula (F-4) are described in International Publication No. 2005/113690.

Hereinafter, a compound having an average value of 6 in F (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ )-is described as "HFPO-", and-(CF (CF ₃ ) CF ₂ O ) _p CF (CF ₃ )-Compounds having an average value of p of 6 to 7 are described as "-HFPO-" and specific compounds of formula (F-4) are shown, but they are not limited to these compounds.

(D-1): HFPO-CONH-C- (CH ₂ OCOCH = CH ₂ ) ₂ CH ₂ CH ₃ (d-2): HFPO-CONH-C- (CH ₂ OCOCH = CH ₂ ) ₂ H (d- 3): 1: 1 Michael addition polymer of HFPO-CONH-C ₃ H ₆ NHCH ₃ and trimethylolpropane triacrylate (d-4): (CH ₂ = CHCOOCH ₂ ) ₂ HC-CONH-HFPO -CONH-C- (CH ₂ OCOCH = CH ₂ ) ₂ H (d-5): (CH ₂ = CHCOOCH ₂ ) ₃ -C-CONH-HFPO-CONH-C- (CH ₂ OCOCH = CH ₂ ) ₃

Furthermore, as a compound represented by a formula (F-4), the compound represented by a following formula (F-5) can also be used.

Formula (F-5): CH ₂ = CX ₁ -COO-CHY-CH ₂ -OCO-CX ₂ = CH ₂ (wherein X ₁ and X ₂ each independently represent a hydrogen atom or a methyl group, and Y represents 3 (Fluoroalkyl groups having 2 to 20 carbon atoms or more or fluorine cycloalkyl groups having 4 to 20 carbon atoms having 4 or more fluorine atoms)

In the present disclosure, a compound having a polymerizable unsaturated group as a (meth) acrylfluorenyloxy group may have a plurality of (meth) acrylfluorenyloxy groups. The fluorine-containing antifouling agent has a plurality of (meth) acryl fluorenyloxy groups, and when it is hardened, it has a three-dimensional grid structure. The glass transition temperature is high, and the antifouling agent has low transferability. Durability in terms of repeated erasing is improved. Furthermore, a cured film excellent in heat resistance and weather resistance can be obtained.

Specific examples of the compound represented by the formula (F-5) include, for example, di (meth) acrylic acid-2,2,2-trifluoroethyl glycol, and di (meth) acrylic acid- 2,2,3,3,3-pentafluoropropyl ethylene glycol, di (meth) acrylic acid-2, 2, 3, 3, 4, 4, 4-heptafluorobutyl ethylene glycol, di (methyl) Based) acrylic acid-2,2,3,3,4,4,5,5,5-nonafluoropentyl glycol, di (meth) acrylic acid-2,2,3,3,4,4,5 , 5,6,6,6-Undecylfluorohexyl glycol, di (meth) acrylic acid-2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 7- Tridecafluoroheptyl ethylene glycol, di (meth) acrylic acid-2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-pentadecafluorooctane Diethylene glycol, di (meth) acrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctyl ethylene glycol, di (methyl) Base) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl glycol, bis (methyl Based) Acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Undecylfluorodecyl glycol Bis (meth) acrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl glycol , 2-trifluoromethyl-3,3,3-trifluoropropyl ethylene glycol di (meth) acrylate, 3-trifluoromethyl-4,4,4-tri (di) methacrylate Fluorobutyl glycol, bis (methyl ) Acrylic acid-1-methyl-2,2,3,3,3-pentafluoropropyl ethylene glycol, di (meth) acrylic acid-1-methyl-2, 2, 3, 3, 4, 4 When used, 4-heptafluorobutyl glycol and the like can be used alone or as a mixture. When preparing such a di (meth) acrylate, it can be manufactured by a well-known method as listed in Japanese Patent Application Laid-Open No. 6-306326. In this disclosure, diacrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptafluoro Nonyl glycol.

In the present disclosure, the compound having a polymerizable unsaturated group as a (meth) acrylfluorenyloxy group may be a compound having a plurality of (per) fluoroalkyl groups or (per) fluoropolyether groups in one molecule.

The fluorine-containing antifouling agent in the present disclosure may be any one of a monomer, an oligomer, or a polymer. The fluorine-containing antifouling agent preferably further has a substituent that facilitates bond formation or compatibility in the hard coat film. The substituents may be the same or different, and preferably have multiple substituents. Examples of preferred substituents include acrylfluorenyl, methacrylfluorenyl, vinyl, dipropyl, cinnamyl, epoxy, oxetanyl, hydroxy, polyoxyalkylene , Carboxyl, amine and so on. The fluorine-containing antifouling agent may be a polymer with a compound containing no fluorine atom, or may be an oligomer.

In addition, the fluorine-containing compound may contain a silicon atom in the molecule, may contain a siloxane structure, and may have a structure other than a siloxane structure. However, when the fluorine-containing compound having a polymerizable unsaturated group contains a siloxane structure, the weight average molecular weight is less than 15,000.

When the fluorine-containing compound contains a siloxane structure, the fluorine-containing compound is preferably represented by the following formula (F-6).

Formula (F-6): R _a R ^f _b R ^A _c SiO _{(4-abc) / 2} (where R is a hydrogen atom, methyl, ethyl, propyl or phenyl, and R ^f is a fluorine atom Organic group, R ^A is an organic group containing a polymerizable unsaturated group, 0 <a, 0 <b, 0 <c, a + b + c <4)

A is preferably 1 to 1.75, more preferably 1 to 1.5. If a is 1 or more, it is easy to synthesize compounds industrially, and if it is 1.75 or less, it is easy to have both hardenability and antifouling properties.

Polymerizable unsaturated group R ^A as a polymerizable unsaturated group, include the same as those in the formula (F.) R ^A, preferably (meth) Bing Xixi group, (meth) yloxy Bing Xixi In addition, any of these groups is substituted with a fluorine atom.

In the case where the fluorine-containing compound contains a siloxane structure, as a preferable example of the siloxane structure, a terminal and / or a side chain of a compound chain including a plurality of dimethylsilyloxy units as repeating units can be cited. Structure with substituents. The compound chain containing dimethylsilyloxy as a repeating unit may also contain structural units other than dimethylsilyloxy. The substituents may be the same or different, and preferably have a plurality of substituents. Examples of preferred substituents include (meth) acrylfluorenyl, (meth) acrylfluorenyloxy, vinyl, allyl, cinnamyl, epoxy, and oxetanyl A group such as hydroxy, fluoroalkyl, polyoxyalkylene, carboxyl, or amine is particularly preferably a (meth) acrylfluorenyloxy group from the viewpoint of suppressing bleeding of the antifouling agent. The number of substituents is preferably 1500 g ･ mol ^-1 to 20,000 g ･ mol ^-in terms of functional group equivalents, from the viewpoints of improving the biased existence of the antifouling agent and suppressing the bleeding of the antifouling agent. ¹ .

R ^f is an organic group containing a fluorine atom, and is preferably a group represented by C _x F _{2x + 1} (CH ₂ ) _p- (wherein x is an integer of 1 to 8 and p is an integer of 2 to 10) Or an alkyl substituted with a perfluoropolyether. b is preferably 0.2 to 0.4, more preferably 0.2 to 0.25. If b is 0.2 or more, the antifouling property is improved, and if it is 0.4 or less, the hardenability is improved. R ^{f is} preferably a perfluoroalkyl group having 8 carbon atoms.

R ^A is an organic group containing a (meth) acrylic group, and in terms of ease of industrial synthesis, a bond with a Si atom is more preferably a Si-OC bond. c is preferably 0.4 to 0.8, and more preferably 0.6 to 0.8. When c is 0.4 or more, the hardenability is improved, and when it is 0.8 or less, the antifouling property is improved.

In addition, a + b + c is preferably 2 to 2.7, and more preferably 2 to 2.5. If a + b + c is less than 2, it is difficult to cause the surface deviation to exist, and if it is greater than 2.7, it is not possible to have both hardenability. Antifouling.

In the case where the fluorine-containing compound contains a siloxane structure, the fluorine-containing compound preferably contains 3 or more F atoms and 3 or more Si atoms in one molecule, and preferably contains 3 to 17 F atoms and 3 ~ 8 Si atoms. If it has 3 or more F atoms, the antifouling property is sufficient, and if it has 3 or more Si atoms, the deviation toward the surface can be promoted, and the antifouling property is sufficient.

When the fluorine-containing compound contains a siloxane structure, the fluorine-containing compound can be produced by using a known method and the like listed in Japanese Patent Laid-Open No. 2007-145884.

When the fluorine-containing compound contains a siloxane structure, the siloxane structure may be any of a linear, branched, and cyclic structure, and among these, a compound having a branched or cyclic structure is particularly preferred. It is preferable because it has good compatibility with a compound having an unsaturated double bond to be described later, has no shrinkage, and is liable to cause a deviation toward the surface.

Here, as the compound having a branched siloxane structure, a compound represented by the following formula (F-7) is preferred. Formula (F-7): R ^f SiR _k [OSiR _m (OR ^A ) _3-m ] _3-k (where R, R ^f and R ^A are the same as above, m = 0, 1 or 2, especially m = 2, k = 0 or 1)

The compound having a siloxane structure having a cyclic structure is preferably a compound in the following formula (F-8). Formula (F-8): (R ^f RSiO) (R ^A RSiO) _n (where R, R ^f and R ^A are the same as above, n ≧ 2, especially 3 ≦ n ≦ 5)

Specific examples of such a fluorine-containing polysiloxane compound include the following compounds.

[Chemical 11]

The weight average molecular weight (Mw) of the fluorine-containing antifouling agent can be measured using molecular exclusion chromatography, for example, Gel Permeation Chromatography (GPC). The Mw of the fluorine-containing antifouling agent that can be used in the hard coat layer of the present disclosure is preferably 400 or more and less than 5,000, more preferably 1,000 or more and less than 5,000, and even more preferably 1,000 or more and less than 3500. When Mw is 400 or more, the surface mobility of the antifouling agent becomes high, which is preferable. In addition, if Mw is less than 5000, the surface mobility of the fluorine-containing antifouling agent is not hindered from coating to the hardening step, and it is easy to align uniformly on the surface of the hard coating layer. Therefore, the antifouling property and film hardness are improved. Better. In the case where the fluorine-containing compound contains a siloxane structure, Mw is less than 15,000, preferably 1,000 or more and less than 5,000, and more preferably 1,000 or more and less than 3500.

The addition amount of the fluorine-containing antifouling agent is preferably 1% to 20% by mass, and more preferably 1% to 15% by mass based on the total solid content in the hard coat layer or the composition for forming the hard coat layer. More preferably, it is 1 to 10 mass%. When the amount of the fluorine-containing antifouling agent is 1% by mass or more relative to the total solid content in the hard coat layer or the composition for forming the hard coat layer, the proportion of the antifouling agent having water and oil repellency is moderate, and Obtain sufficient antifouling properties. In addition, if the amount of the fluorine-containing antifouling agent is 20% by mass or less based on the total solid content in the hard coat layer or the composition for forming a hard coat layer, the antifouling agent that cannot be mixed with the resin component will not precipitate It is preferable that the film does not whiten or produce white powder on the surface.

The fluorine atom content of the fluorine-containing antifouling agent is not particularly limited, but it is preferably 20% by mass or more, particularly preferably 30% to 70% by mass, and most preferably 40% to 70% by mass.

As examples of preferred fluorine-containing antifouling agents, R-2020, M-2020, R-3833, M-3833, and Optool DAC (manufactured by Daikin) The above are trade names), Megafac (registered trademark) F-171, F-172, F-179A, Defensa MCF-300, MCF-323 (above) Is a product name), but is not limited to these examples.

[Polysiloxane compound having a polymerizable unsaturated group having a weight average molecular weight of 15,000 or more] Next, a polysiloxane having a polymerizable unsaturated group having a weight average molecular weight of 15,000 or more that can be used as a component g) The compounds are explained. The polysiloxane compound having a molecular weight of 15,000 or more is hereinafter referred to as a "polysiloxane antifouling agent".

One aspect of a preferable example of the polysiloxane antifouling agent is a compound represented by the formula (F-6).

As a preferable example of a polysiloxane antifouling | staining agent, the compound which has a substituent in the terminal and / or side chain of the compound chain which contains several dimethylsilyloxy unit as a repeating unit is mentioned. The compound chain containing dimethylsilyloxy as a repeating unit may also contain structural units other than dimethylsilyloxy. The substituents may be the same or different, and preferably have a plurality of substituents. Examples of preferred substituents include (meth) acrylfluorenyl, (meth) acrylfluorenyloxy, vinyl, allyl, cinnamyl, epoxy, and oxetanyl A group such as hydroxy, fluoroalkyl, polyoxyalkylene, carboxyl, or amine is particularly preferably a (meth) acrylfluorenyloxy group from the viewpoint of suppressing bleeding of the antifouling agent. The number of substituents is preferably from 1500 g ･ mol ^-1 to 20000 g ･ mol ^{-1 in} terms of functional group equivalents from the viewpoint of improving the biased existence of the antifouling agent and suppressing the bleeding of the antifouling agent. .

The polysiloxane antifouling agent is preferably a compound containing 3 or more F atoms and 3 or more Si atoms in one molecule, and more preferably 3 to 17 F atoms and 3 to 8 Si atoms. If it has 3 or more F atoms, the antifouling property is sufficient, and if it has 3 or more Si atoms, the deviation toward the surface can be promoted, and the antifouling property is sufficient.

The polysiloxane antifouling agent can be produced using known methods and the like listed in Japanese Patent Laid-Open No. 2007-145884. As an additive having a polysiloxane structure, polysiloxane containing reactive groups such as "KF-100T", "X-22-169AS", "KF-102", "X-22-3701IE", "X-22-164C", "X-22-5002", "X-22-173B", "X-22-174D", "X-22-167B", "X-22-161AS" (brand name ), The above is manufactured by Shin-Etsu Chemical Industry (Stock); "AK-5", "AK-30", "AK-32" (trade name), the above is manufactured by East Asia Synthetic (Stock); "Silaplane ) FM0725 "," Silaplane FM0721 "(trade name), the above are manufactured by Chisso (shares);" DMS-U22 "," RMS-033 "," UMS-182 "(commodity Name), the above are made by Gelest, etc. are also better. In addition, the silicone compounds described in Table 2 or Table 3 of Japanese Patent Application Laid-Open No. 2003-112383 can also be preferably used.

The siloxane structure contained in the polysiloxane antifouling agent may be any of linear, branched, and cyclic. Among these, compounds having a branched or cyclic structure are particularly The compounds and the like having unsaturated double bonds described later are excellent in compatibility, non-shrinkage, and tend to cause a deviation toward the surface, which is preferable.

The weight average molecular weight of the polysiloxane antifouling agent is 15,000 or more, preferably 15,000 or more and 50,000 or less, and more preferably 18,000 or more and 30,000 or less. If the weight average molecular weight of the polysiloxane antifouling agent is less than 15,000, deterioration of antifouling properties and reduction in hardness due to a decrease in the existence of the surface deviation of the polysiloxane will be unfavorable from this viewpoint. However, the problem is not caused when the fluorine-containing compound having a polymerizable unsaturated group has a polysiloxane structure. The weight average molecular weight of the polysiloxane antifouling agent can be measured using molecular exclusion chromatography, for example, gel permeation chromatography (GPC).

The addition amount of the polysiloxane antifouling agent is preferably 1% by mass or more and less than 25% by mass, and more preferably 1% by mass or more, based on the total solid content in the hard coat layer or the composition for forming the hard coat layer. It is less than 20% by mass, more preferably 1% by mass or more and less than 15% by mass, and most preferably 1% by mass or more and less than 10% by mass. When the polysiloxane antifouling agent is added in an amount of 1% by mass or more with respect to the total solid content in the hard coat layer or the composition for forming a hard coat layer, the proportion of the antifouling agent having water and oil repellency is moderate. To obtain sufficient antifouling properties. In addition, if the amount of the polysiloxane antifouling agent is less than 25% by mass based on the total solid content in the hard coat layer or the composition for forming the hard coat layer, the antifouling agent that cannot be mixed with the resin component will not be mixed. It will be deposited on the surface, and it will not cause whitening of the film or white powder on the surface, so it is preferable.

When X is the amount of fluorine or silicone in the vicinity of the surface of the hard coat layer, and Y is the amount of fluorine or silicone in the entire hard coat layer, the antifouling agent in the hard coat layer is in the film thickness direction. The distribution state on the surface is preferably such that 51% <X / Y <100%. In the case where X / Y is more than 51%, the antifouling agent is not distributed to the inside of the film of the hard coat layer, and it is preferable in terms of antifouling property and film hardness. The term “near the surface” refers to a region with a depth of less than 1 μm from the surface of the hard coat layer. It can be analyzed by using time-of-flight secondary ion mass spectrometry (TOF-SIMS). The F ^- fragment or Si ₂ C ₅ H ₁₅ O ⁺ fragment ratio was measured.

g) The antifouling agent is preferably an antifouling agent dissolved in a liquid or a solvent at 20 ° C. The solvent may be appropriately selected depending on the polarity of the compound, and an organic solvent mixed with dimethyl carbonate is preferred. Examples of the solvent include aliphatic or reporter alcohol, ketone, ester, and ether solvents. It is particularly preferred if it is dissolved in dimethyl carbonate. Regarding the surface tension of the antifouling agent, from the viewpoint of antifouling properties, the surface tension is preferably 25.0 mN / m or less, more preferably 23.0 mN / m or less, and even more preferably 16.0 mN / m or less. The surface tension of the antifouling agent is the surface tension in a single film, and can be measured as follows.

(Method for measuring surface tension of antifouling agent) The antifouling agent was spin-coated on a quartz substrate and dried with a solvent to produce a film. Then, using a contact angle meter ["CA-X" type contact angle meter, manufactured by Kyowa Interface Science (Stock)], in a dry state (20 ° C / 65% RH), using pure water as a liquid to form a diameter on the needle tip A 1.0 mm droplet was brought into contact with the surface of the spin-coated film to form a droplet on the film. Of the points where the film is in contact with the liquid, the angle of the side containing the liquid among the angles formed by the tangent to the liquid surface and the surface of the film was measured as the contact angle. In addition, instead of water, diiodomethane was used to measure the contact angle, and the surface free energy was determined by the following formula. Surface free energy: the value ^{γs v (= γs d + γs} h) (γs v units of mN / m) and is made γs ^d and γs ^h is defined indicated, the γs ^d and γs ^h is DK Owens DKOwens: Journal of Applied Polymer Science (J.Appl.Polym.Sci.) 13,1741 (1969) as a reference, based on experimentally obtained pure water on an antireflection film The contact angles θ _H2O and θ _{CH2I2 of} H ₂ O and diiodomethane CH ₂ I ₂ are _determined by the following simultaneous equations a and b. a.1 + cosθ _H2O = 2√γs ^d (√γ _H2O ^d / γ _H2O ^v ) + 2√γs ^h (√γ _H2O ^h / γ _H2O ^v ) b.1 + cosθ _CH2I2 = 2√γs ^d (√γ _CH2I2 ^d / γ _CH2I2 ^v ) + 2√γs ^h ( _{√γ CH2I2} ^h / γ _CH2I2 ^v ) γ _H2O ^d = 21.8, γ _H2O ^h = 51.0, γ _H2O ^v = 72.8, γ _CH2I2 ^d = 49.5, γ _CH2I2 ^h = 1.3, γ _CH2I2 ^v = 50.8

As the antifouling agent g) described above, a compound synthesized by a known method may be used, or a commercially available product may be used. As commercially available products, RS-90, RS-78, etc. manufactured by DIC Corporation can be preferably used.

(Solvent) The composition for forming a hard coat layer may contain a solvent. As a solvent, various solvents can be used as long as they can dissolve or disperse each component; easily form uniform surface properties in the coating step and drying step; ensure liquid storage; and have a moderate saturation vapor pressure. . The solvent may be used in combination of two or more solvents. In particular, from the viewpoint of a drying load, a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature as a main component is preferable, and a solvent having a boiling point exceeding 100 ° C. is contained in a small amount in order to adjust the drying rate. In the composition for forming a hard coat layer, 30% to 80% by mass of all solvents containing the coating composition are preferably solvents having a boiling point of 80 ° C or lower, and more preferably 50% to 70% by mass. . By setting the solvent ratio having a boiling point of 80 ° C. or lower to the above ratio, the infiltration of the resin component into the polyester film can be moderately suppressed, and by increasing the drying viscosity increase rate, particle sedimentation can be suppressed.

Examples of solvents having a boiling point of 100 ° C or lower are listed below. It should be noted that the temperature described together is the boiling point of each solvent. Examples of solvents having a boiling point of 100 ° C or lower include hydrocarbons such as hexane (68.7 ° C), heptane (98.4 ° C), cyclohexane (80.7 ° C), benzene (80.1 ° C), and dichloromethane (39.8 ° C) , Halogenated hydrocarbons such as chloroform (61.2 ℃), carbon tetrachloride (76.8 ℃), 1,2-dichloroethane (83.5 ℃), trichloroethylene (87.2 ℃), diethyl ether (34.6 ℃), Ethers such as diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), tetrahydrofuran (66 ° C), ethyl formate (54.2 ° C), methyl acetate (57.8 ° C), ethyl acetate (77.1 ° C) ), Esters such as isopropyl acetate (89 ° C), ketones such as acetone (56.1 ° C), 2-butanone (methyl ethyl ketone: hereinafter sometimes referred to as MEK, 79.6 ° C), methanol (64.5 ° C) , Alcohols (78.3 ° C), 2-propanol (82.4 ° C), 1-propanol (97.2 ° C), cyano compounds such as acetonitrile (81.6 ° C), propionitrile (97.4 ° C), carbon disulfide (46.2 ° C) Wait. Among them, ketones and esters are preferred, and ketones are particularly preferred. Among the ketones, 2-butanone is particularly preferred.

Examples of solvents having a boiling point exceeding 100 ° C include octane (125.7 ° C), toluene (110.6 ° C), xylene (138 ° C), tetrachloroethylene (121.2 ° C), chlorobenzene (131.7 ° C), and dioxane (101.3 ℃), dibutyl ether (142.4 ℃), isobutyl acetate (118 ℃), cyclohexanone (155.7 ℃), 2-methyl-4-pentanone (methyl isobutyl ketone: hereinafter sometimes called MIBK, 115.9 ° C), 1-butanol (117.7 ° C), N, N-dimethylformamide (153 ° C), N, N-dimethylacetamide (166 ° C), dimethylene碸 (189 ° C) and so on. Cyclohexanone and 2-methyl-4-pentanone are preferred.

(Surfactant) It is also suitable to use various surfactants, wind-induced unevenness prevention agents, and the like (hereinafter, collectively referred to as surfactants) in the hard coat layer or the composition for forming a hard coat layer. In general, by including a surfactant or a wind-induced unevenness preventing agent, uneven film thickness due to uneven drying due to the local distribution of dry wind can be suppressed.

As the surfactant, specifically, at least one of a fluorine-based surfactant and a silicone-based surfactant is preferably contained. In addition, with regard to surfactants, oligomers or polymers are superior to low molecular compounds.

Preferable examples of the fluorine-based surfactant include, for example, a copolymer containing a fluorinated aliphatic group (hereinafter, sometimes referred to simply as a “fluorine-based polymer”), and the above-mentioned fluorine-based polymer is useful Acrylic resin and methacrylic acid containing a repeating unit corresponding to the monomer (i) below or a repeating unit corresponding to the monomer (i) and further including a repeating unit corresponding to the monomer (ii) below Copolymers of resins and vinyl monomers copolymerizable with them.

(I) a fluorine-containing aliphatic group monomer represented by the following formula (i-1)

[Chemical 12]

In formula (i-1), R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom, or -N (R ¹² )-, m represents an integer of 1 to 6, and n represents 2 to 4 Integer. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, and a hydrogen atom or a methyl group is preferred. X is preferably an oxygen atom.

(Ii) A monomer represented by the following formula (ii-1) which can be copolymerized with the above (i): Formula (ii-1)

[Chemical 13]

In formula (ii-1), R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom, or -N (R ¹⁵ )-, and R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically, A methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a hydrogen atom or a methyl group is preferable. Y is preferably an oxygen atom, -N (H) - and -N (CH ₃₎ -. R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 or more and 20 or less carbon atoms which may have a substituent. Examples of the substituent of the alkyl group of R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyanide group. Group, amino group, and the like, but are not limited thereto. As the linear, branched, or cyclic alkyl group having 4 to 20 carbon atoms, a linear and branchable butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, tetradecyl, fifteen, octadecyl, icosyl, etc., and monocyclic cycloalkyl and bicycloheptyl, bicyclodecyl, etc. such as cyclohexyl and cycloheptyl , Tricyclic undecyl, tetracyclododecyl, adamantyl, norbornyl, tetracyclodecyl and other polycyclic cycloalkyl.

The amount of the fluorine-containing aliphatic group-containing monomer represented by formula (i-1) used in the fluorine-based polymer is 10 mol% or more based on each monomer of the fluorine-based polymer. It is preferably in the range of 15 mol% to 70 mol%, and more preferably in the range of 20 mol% to 60 mol%.

The preferred mass average molecular weight of the fluoropolymer is preferably 3000 to 100,000, and more preferably 5,000 to 80,000. Furthermore, with respect to 100 parts by mass of the coating liquid, the preferable addition amount of the fluoropolymer is in the range of 0.001 to 5 parts by mass, more preferably in the range of 0.005 to 3 parts by mass, and still more preferably 0.01 part by mass The range is from 1 part by mass. If the addition amount of the fluorine-based polymer is 0.001 parts by mass or more, the effect after the addition of the fluorine-based polymer is sufficiently obtained, and if it is 5 parts by mass or less, the following problem does not occur: drying of the coating film is not sufficiently performed Or adversely affect the performance as a coating film.

Examples of preferred silicone compounds include X-22-174DX, X-22-2426, X22-164C, and X-22-176D (the above are trade names) manufactured by Shin-Etsu Chemical Industry Co., Ltd .; FM-7725, FM-5521, FM-6621 (above are the trade names) manufactured by Chisso (shares); DMS-U22, RMS-033 (the above are trade names) manufactured by Gelest; SH200, DC11PA, ST80PA, L7604, FZ-2105, L-7604, Y-7006, SS-2801 (above are the trade names) manufactured by Toray Dow Corning (shares); Japan Momentive Advanced Materials (Momentive · High performance · Materials · Japan) and the like are not limited to these examples. When the total solid content of the composition for forming a hard coat layer is 100% by mass, it is preferable to contain 0.01 to 0.5% by mass of a silicone-based surfactant, and more preferably 0.01 to 0.3% by mass. %.

(Matting particles) The composition for forming a hard coat layer or a hard coat layer may provide internal scattering properties or surface unevenness, and may also contain an average particle diameter of 1.0 μm to 15.0 μm, preferably 1.5 μm to 10.0. μm matting particles. In addition, in order to adjust the viscosity of the coating liquid, a polymer compound or an inorganic layered compound may be included. It is also possible to use e) as matting particles.

[Coating method of hard coat layer] The hard coat layer in the decorative film of the present disclosure can be formed by the following method, for example. First, a composition for forming a hard coat layer is prepared. Next, the prepared composition for forming a hard coat layer is coated on a substrate film, and then heated and dried. The drying method will be described later. Examples of the coating method of the composition on the support include a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a wire rod coating method, a gravure coating method, and a micro gravure coating method. Method, die coating method, etc. Among these, a micro gravure coating method, a wire rod coating method, and a die coating method are preferable, and a die coating method is more preferable. The details of the die coating method are described in detail in, for example, U.S. Patent No. 2,681,294 and Japanese Patent Laid-Open No. 2006-122889, and these references can be referred to.

After the composition for forming a hard coat layer is coated on a substrate film and dried, the solvent contained in the composition is removed, and the composition for forming a hard coat layer is hardened to form a hard coat layer. For example, the base film on which the composition layer for forming a hard coat layer is formed is transported and passed through a heated area to be dried. The temperature in the drying area used for drying is preferably 25 ° C to 140 ° C. The temperature in the drying area may not necessarily be uniform. It is preferable that the first half of the drying area is a relatively low temperature, such as a range of 25 ° C to 100 ° C, and the second half is a relatively high temperature, such as 60 ° C to 140 ° C. Range. Among them, the temperature in the dry region is preferably equal to or lower than a temperature at which components other than the solvent contained in the layer other than the composition layer for forming a hard coat layer formed on the support and the layer other than the composition layer for forming a hard coat layer are volatilized. . More specifically, for example, a commercially available photo-radical generator used in combination with an ultraviolet curable resin has a compound that volatilizes in a warm air at 120 ° C in about 10% of its amount within a few minutes, and A monofunctional acrylate monomer, a bifunctional acrylate monomer, and the like have a compound that volatilizes in a warm air at 100 ° C. When these compounds which are easily volatile at a heating temperature of about 100 ° C are used for the composition for forming a hard coat layer, the temperature in the heating region is preferably equal to or higher than the volatilization temperature of the solvent and components other than the solvent start to volatilize. Below the temperature.

When the composition for forming a hard coat layer is applied to a base film after drying the composition layer for forming a hard coat layer by blowing dry air to dry it, in order to prevent the composition layer for forming a hard coat layer from drying, When the solid content concentration of the composition for forming a hard coat layer is 1% to 50% by mass, the wind speed on the surface of the coating film of the composition for forming a hard coat layer is preferably 0.1 m / sec to 2 m / sec. In the range. In addition, as another preferable example of the drying conditions, the following method may be mentioned: after the composition layer for forming a hard coat layer is coated on a substrate film, the composition is coated with the substrate film in a dry area. The temperature difference between the temperature of the conveying roller and the temperature of the base film which are in contact with the opposite surface of the surface is adjusted to be within 0 ° C to 20 ° C. By setting the temperature difference between the transfer roller and the base film to the above range, uneven drying of the hard coat layer due to uneven heat transfer on the transfer roller can be prevented, which is preferable.

In the dry region, after removing the solvent from the composition for forming a hard coat layer, the composition layer for forming a hard coat layer on the substrate film is passed through a hardened region where the hard coat layer is hardened by irradiation with ionized radiation. , So that the hard coating can be hardened. When the composition for forming a hard coat layer is an ultraviolet-curable composition, the hardened region is preferably a region irradiated with an ultraviolet lamp. The irradiation amount of the ultraviolet lamp is preferably in a range of 10 mJ / cm ² to 1000 mJ / cm ² . By irradiating ultraviolet rays at the above-mentioned irradiation amount, the hard coat layer can be suitably cured. When the ultraviolet irradiation is performed, the irradiation amount distribution in the width direction of the composition layer for forming a hard coat layer on the support carried in the hardened region on the support is preferably relative to the maximum ultraviolet irradiation amount in the center, including two The distribution at the ends is 50% to 100%, more preferably the distribution is 80% to 100%. In order to suppress the hardening barrier caused by oxygen in the ultraviolet-curable composition and further promote the hardening of the surface of the hard coat layer, an inert gas such as nitrogen may be purged in the hardened area to reduce the oxygen concentration. The oxygen concentration when reducing the oxygen concentration is preferably 0.01% to 5%, and the distribution in the width direction of the oxygen concentration in the hardened region is preferably 2% or less. In order to accelerate the curing reaction of the ultraviolet-curable composition, the temperature in the curing region can be increased. From the viewpoint of accelerating the hardening reaction, the temperature in the hardened region is preferably set to 25 ° C to 100 ° C, more preferably 30 ° C to 80 ° C, and even more preferably 40 ° C to 70 ° C.

When forming a hard coat layer, other functional layers may be provided as needed. When the hard coat layer is formed, in the case where other functional layers are laminated in addition to the hard coat layer, multi-layer coating in which a plurality of layers are simultaneously applied may be performed, and sequential coating may be performed. The formation of any other functional layer can be performed in accordance with the manufacturing method of the hard coat layer described above. Examples of other functional layers that can be provided when forming the hard coat layer include an easy-adhesion layer, a refractive index adjustment layer, and an ultraviolet absorbing layer.

[Decorative layer] The decorative film of the present disclosure has a decorative layer. The decorative layer has a decorative layer in at least a part of the entire area of the decorative film in a plan view. The decoration layer may be provided on the entire surface of the substrate or a part thereof. The decorative layer imparts various design properties to the decorative film. Examples of the decoration layer include characters or graphics that are visually recognized around the image display portion when used as an image display panel, or a black fringe-shaped decoration layer provided in a frame shape on the image display portion. FIG. 3 is a plan view showing an aspect of the decorative film 10 of the present disclosure. Among them, as shown in FIG. 3, the decoration layer 14 of the decoration film 10 is preferably provided in the image display portion on a peripheral edge portion of the decoration film 10 in a plan view. That is, it is preferable to provide a black frame-shaped light-shielding layer on the back side of the base material including the transparent polyester film, that is, the side where the decorative film is mounted, to hide the internal wiring, etc., and improve it. Appearance of tablet terminals and the like.

The decorative layer may be formed as a resin layer containing a colorant corresponding to a purpose. The coloring agent contained in the decorative layer can be appropriately selected from various coloring agents according to the purpose of use. In general, when the decorative layer is used as a light-shielding layer, a light-shielding coloring agent such as a black pigment is used, and when the decorative layer is provided as a background color on the entire surface of the decorative film, a white pigment is used. Examples of the black pigment contained in the decorative layer include carbon black, titanium black, and the like, all of which have good light-shielding properties, and are preferably used as light-shielding layers. Examples of the white pigment include titanium oxide and zinc oxide.

As for the decorative layer, the composition for forming a decorative layer containing a colorant and a binder resin can be provided in a pattern by applying a printing method to the surface of a substrate including a hard coat layer or a polyester film, for example. Transfer method to set. In addition, it may be provided by forming and patterning a composition for forming a positive or negative decorative layer on the surface of a substrate including a hard coat layer or a polyester film. Examples of the composition for forming a positive decorative layer include a composition containing a compound that improves the solubility of the binder resin, such as a colorant, a binder resin, and a photoacid generator. Examples of the composition for forming a negative decorative layer include a composition containing a colorant, a polymerizable compound having an ethylenically unsaturated group, and a polymerization initiator.

As a method of providing a decorative layer, any of a printing method and a transfer method can be used. Examples of the material for forming the decorative layer include printing inks containing a colorant that can be used to form a colored film on a resin substrate. From the viewpoint of simplicity, it is also preferable to use a printing ink containing a coloring agent as described in the formation of the decorative layer by a printing method. Examples of the printing method include a screen printing method, a screen printing method, an inkjet printing method, a gravure printing method, and a thermal transfer printing method. Among these, a screen printing method, a screen printing method, and a thermal transfer printing method are preferred from the viewpoint that a decorative layer with good concealment can be printed. By the printing method, a decorative layer can be easily provided in a pattern on the entire surface or a desired area.

As the printing ink used when the decorative layer is formed by the screen printing method or the screen printing method, various inks used for printing on a film can be used, and a solvent-based or UV-curable system can be used. In particular, the solvent-based ink uses a drying oven to dry the solvent. Therefore, a device such as a UV irradiation device is not required and printing can be performed at low cost. Therefore, it can be used suitably. As the ink used in the thermal transfer method, a resin type or a wax type can be used. Among them, the resin type is suitably used because of its excellent weather resistance.

The decorative layer for forming a patterned positive or negative decorative layer may be applied to at least one surface of a substrate including a polyester film by a coating method, a transfer method, or the like to form a decorative layer. The composition layer is formed, and a pattern-like decorative layer is formed by pattern exposure and development in which exposure is performed through a mask. By patterning by exposure, a desired pattern with high resolution can be formed.

The thickness of the decorative layer is preferably 40 μm or less, more preferably 1 μm to 25 μm, and particularly preferably 2 μm to 20 μm. By setting the thickness of the decorative layer to the range described above, it is difficult to cause discoloration or poor printing, and it is easy to obtain suitable designability.

Examples of preferred layer configurations of the decorative film of the present disclosure are shown below, but are not limited to these layer configurations. The following layer configurations are described in order from the member side provided with the decorative film. · Decorative layer / Substrate including polyester film / Hard coating · Substrate including polyester film / Hard coating / Decorative layer · Substrate including polyester film / Decorative layer / Hard coating From the viewpoint of scratch resistance, it is preferable that the decorative layer is disposed on one surface of the polyester film, and the hard coat layer is disposed on the surface of the polyester film opposite to the surface on which the decorative layer is disposed. That is, it is preferable to have a decorative layer in close proximity to a member provided with the decorative film of the present disclosure, and to sequentially have a polyester film as a base material and an outermost hard coat layer in this order.

FIG. 3 is a plan view showing an embodiment of a formation region of the decoration layer 14 in the decoration film 10. In FIG. 3, the decorative layer 14 is provided on a peripheral edge portion of the decorative film 10. In the non-formed region of the decoration layer 14, the polyester film and the hard coat layer can be seen from a top view.

4A, 4B, and 4C are schematic side views showing modified examples of a multilayer structure of a decorative layer / a substrate including a polyester film / a hard coat layer. The decorative film 10 shown in FIG. 4A has a state in which a decorative layer 14, a base material 16 including a polyester film, and a hard coat layer 18 are laminated in this order from the member side on which the decorative film 10 is arranged, that is, the lower portion of FIG. 4A. The decorative film 20 shown in FIG. 4B has a state in which a substrate 16 including a polyester film, a hard coat layer 18 and a decorative layer 14 are laminated in this order from the member side on which the decorative film 20 is arranged. The decorative film 22 shown in FIG. 4C has a state in which a base material 16 including a polyester film, a decorative layer 14 and a hard coat layer 18 are laminated in this order from the member side where the decorative film 22 is disposed. The decorative film of the present disclosure may have any of the laminated structures described above. The decorative film may have any layer other than the base material 16, the hard-coat layer 18, and the decorative layer 14 including a polyester film as needed.

5A and 5B show a modified example of a schematic cross-sectional view on the A-A line of the decorative film 10 shown in FIG. 4A. The decorative film 22 shown in FIG. 4A shows the same laminated structure as the side view shown in FIG. 4C, and has a substrate 16 including a polyester film on the side where the decoration film is disposed, and a surface of the substrate 16 including the polyester film. The one-sided peripheral portion has a patterned decorative layer 14 having a shape as shown in FIG. 3 in plan view, and a hard coat layer 18 on a side of the base material 16 including the polyester film provided with the decorative layer 14. In the decorative film 10 shown in FIG. 5B, the peripheral edge portion of the surface on the member-side where the decorative film 10 is arranged as one side of the base material 16 including the polyester film has a structure shown in FIG. 3 in a plan view. Shaped decorative layer 14. A hard coat layer 18 is provided on a surface of the base material 16 including the polyester film on the side opposite to the surface having the decorative layer 14. In addition, the layer configuration of the decorative layer is not limited to the examples described above, and various modifications can be adopted.

The decorative film of the present disclosure may include other layers (arbitrary layers) in addition to the polyester film, the decorative layer, and the hard coat layer. Examples of arbitrary layers include refractive index adjustment layers such as an easy-adhesion layer, an anti-reflection layer (a laminated film of one or more high refractive index layers and one or more low refractive index layers), an anti-glare layer, and a low refractive index layer, The antistatic layer, the ultraviolet absorbing layer, and the like are not limited to these layers. Regarding the arbitrary layer, for example, the descriptions in paragraphs 0069 to 0091 of Japanese Patent No. 5048304 can be referred to.

(Low-refractive index layer) In the decorative film of the present disclosure, a low-refractive index layer may be formed on the hard coat layer for the purpose of imparting a reflectance-reducing effect. The low refractive index layer is a layer having a lower refractive index than the hard coat layer. When a low refractive index layer is provided on the surface of the hard coat layer, the thickness of the low refractive index layer is preferably 50 nm to 200 nm, more preferably 70 nm to 150 nm, and even more preferably 80 nm to 120 nm. .

The refractive index of the low refractive index layer is preferably lower than the refractive index of the layer immediately below. The refractive index of the low refractive index layer is preferably 1.20 to 1.55, more preferably 1.25 to 1.46, and even more preferably 1.30 to 1.40. When the low refractive index layer is provided, the thickness of the low refractive index layer is preferably 50 nm to 200 nm, and more preferably 70 nm to 100 nm. The low refractive index layer is preferably obtained by curing a curable composition for forming a low refractive index layer. Preferred aspects of the curable composition for forming a low-refractive index layer include: (1) a composition containing a fluorine-containing compound having a crosslinkable functional group or a polymerizable functional group, (2) A composition containing a hydrolyzed condensate of a fluorine-containing organosilane material as a main component, and (3) a monomer containing two or more ethylenically unsaturated groups and inorganic particles (particularly, inorganic particles having a hollow structure) The composition here is preferably an inorganic particle having a hollow structure as the inorganic particle). It is also preferable that the composition for forming each of the low refractive index layers in (1) and (2) contains inorganic particles. As the inorganic particles, if inorganic particles having a hollow structure having a lower refractive index than solid inorganic particles are used, From the viewpoint of lowering the refractive index or adjusting the addition amount and refractive index of the inorganic particles, it is particularly preferable.

(1) Composition containing a fluorinated compound having a crosslinkable or polymerizable functional group As the fluorinated compound having a crosslinkable or polymerizable functional group, examples of the fluorinated compound having a crosslinkable or polymerizable functional group include A fluorinated polymer of a copolymer of a polymerizable functional group monomer. Specific examples of these fluoropolymers are described in Japanese Patent Laid-Open No. 2003-222702, Japanese Patent Laid-Open No. 2003-183322, and the like.

When the fluoropolymer is used for the formation of a low refractive index layer, it may be appropriately combined with a polymerizable unsaturated group hardener as described in Japanese Patent Laid-Open No. 2000-17028. And use. Further, as described in Japanese Patent Application Laid-Open No. 2002-145952, a compound having a polyfunctional polymerizable unsaturated group and a fluorine-containing polymer in combination with a fluorine-containing polymer is also preferred. Examples of the compound having a polyfunctional polymerizable unsaturated group include the monomer having two or more ethylenically unsaturated groups described as the curable resin of the low refractive index layer. In addition, as a compound for forming a low refractive index layer, a hydrolyzed condensate of an organosilane described in Japanese Patent Laid-Open No. 2004-170901 is also preferable, and a (meth) acrylfluorenyl group-containing one is particularly preferable. Hydrolyzed condensates of organosilanes. In particular, when a compound having a polymerizable unsaturated group in a polymer body is used, these compounds have a large combined effect with respect to improvement of scratch resistance and are preferred.

When the polymer itself does not have sufficient hardenability, it is possible to impart necessary hardenability to the composition for forming a low refractive index layer by blending a crosslinkable compound. For example, when a hydroxyl group is contained in a polymer body, it is preferable to use various amine compounds as a hardener. Examples of the amine-based compound that can be used as the crosslinkable compound include compounds containing one or both of two or more hydroxyalkylamino groups and alkoxyalkylamino groups in total. Specific examples of the amine-based compound used as the crosslinkable compound include melamine-based compounds, urea-based compounds, benzoguanamine-based compounds, and acetylene urea-based compounds. In curing these compounds, an organic acid or a salt thereof is preferably used.

(2) A composition containing a hydrolyzed condensate of a fluorine-containing organosilane material as a main component A composition having a hydrolyzed condensate of a fluorine-containing organosilane compound as a main component has a low refractive index and high hardness on the surface of the coating film. Better. As the fluorine-containing organosilane material, a condensate of a compound containing a hydrolyzable silanol at one or both ends with respect to a fluorinated alkyl group and a tetraalkoxysilane is preferred. Specific compositions are described in Japanese Patent Laid-Open No. 2002-265866 and Japanese Patent No. 317152.

(3) A composition containing a monomer having two or more ethylenically unsaturated groups and inorganic particles having a hollow structure. Further, as another preferable aspect of the low refractive index layer, particles containing low refractive index and Low refractive index layer of resin. The low-refractive index particles contained in the low-refractive index layer may be organic particles or inorganic particles, and are preferably hollow particles having pores inside. Specific examples of the hollow particles include silicon dioxide-based particles described in Japanese Patent Laid-Open No. 2002-79616. The refractive index of the particles used in the low refractive index layer is preferably 1.15 to 1.40, and more preferably 1.20 to 1.30. Examples of the resin used in the low-refractive index layer include resins derived from a monomer having two or more ethylenically unsaturated groups described in the item of the anti-glare layer.

In the composition for forming a low-refractive-index layer, it is preferable to add a photo radical polymerization initiator or a thermal radical polymerization initiator. When the composition for forming a low-refractive-index layer contains a radically polymerizable compound, 1 to 10 parts by mass, preferably 1 to 5 parts by mass, can be used with respect to 100 parts by mass of the radically polymerizable compound. Parts of polymerization initiator.

In the low refractive index layer, inorganic particles may be used in combination. By using inorganic particles in combination, scratch resistance can be imparted to the low refractive index layer. In order to impart scratch resistance to the low refractive index layer, inorganic particles having a particle size of 15% to 150%, preferably 30% to 100%, and more preferably 45% to 60% of the thickness of the low refractive index layer can be used. .

For the purpose of imparting properties such as antifouling properties, water resistance, chemical resistance, and smoothness to the low refractive index layer, known polysiloxane-based antifouling agents, fluorine-based antifouling agents, Smoothing agent and so on.

As an additive having a polysiloxane structure, reactive polysiloxane containing reactive groups such as KF-100T, X-22-169AS, KF-102, X-22-37-01IE, X-22-164B, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (trade names), the above are manufactured by Shin-Etsu Chemical Industry (stock); AK-5, AK- 30. AK-32 (brand name), the above are manufactured by East Asia Synthetic (stock); "Silaplane FM0725", "Silaplane FM0721" (trade name), and the above are JNC (shares ) Manufacturing is also better. In addition, the silicone compounds described in Tables 2 and 3 of Japanese Patent Application Laid-Open No. 2003-112383 can also be preferably used.

The fluorine-based compound is preferably a compound having a fluoroalkyl group. The carbon number of the fluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, and may be a straight chain (for example, -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, -CH ₂ (CF ₂ ) ₈ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), or branch structures (such as CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), can also be alicyclic structure (preferably 5-membered ring or 6-membered ring, such as perfluorocyclohexyl, perfluorocyclopentyl or These substituted alkyl groups, etc.) may also have ether bonds (for example, CH ₂ OCH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

The fluorine-based compound preferably further has a substituent that facilitates formation of a bond or compatibility with the low-refractive-index layer coating. The fluorine-based compound preferably has a plurality of the substituents. When the fluorine-based compound has a plurality of the substituents, the substituents may be the same or different. Preferable examples of the substituent include acrylfluorenyl, methacrylfluorenyl, vinyl, dipropyl, cinnamyl, epoxy, oxetanyl, hydroxyl, and polyoxyalkylene Group, carboxyl group, amine group, etc. The molecular weight of the fluorine compound is not particularly limited. The fluorine-based compound may be a polymer having a partial structure not containing a fluorine atom, or may be an oligomer. The fluorine atom content in the fluorine-based compound is not particularly limited, but it is preferably 20% by mass or more, particularly preferably 30% to 70% by mass, and most preferably 40% to 70% by mass. Examples of preferred fluorine-based compounds include R-2020, M-2020, R-3833, M-3833, and Optool DACs (above: (Trade name), Megafac (registered trademark) F-171, F-172, F-179A, Defensa MCF-300, MCF-323 (the above are products) Name), etc., but not limited to these examples. It is preferable that these polysiloxane fluorinated compounds or compounds having a polysiloxane structure are added in a range of 0.1% to 10% by mass of the total solid content of the low refractive index layer, particularly preferably 1% to 5%. Case of mass%.

[Application of Decorative Film] The application of the decorative film of the present disclosure is not particularly limited, and can be suitably used without particular limitation as long as it is an application that requires scratch resistance and has a requirement for design. In particular, in applications where mounting on components requires press processing, for example, in applications such as image display devices and touch panels, the occurrence of peeling, cracks, and chipping of the decorative layer during processing is suppressed, so it can be said that the effect is significant .

[Manufacturing Method of Decorative Film] The manufacturing method of the decorative film of the present disclosure includes: a polyester film forming step; a decorative layer forming step, forming a decorative layer on at least a part of one surface of the polyester film; and a hard coat layer forming step Forming a hard coat layer on at least one side of the polyester film, the polyester film forming step includes a lateral extension step using a plurality of jigs provided with a pair of rails that are respectively moved along two sides of the film conveying road The tenter-type stretching device stretches the unstretched polyester film in a direction orthogonal to the film conveying road while holding the unstretched polyester film with a clamp; the heat fixing step is performed by The ester film is heated for heat fixing; and a heat relaxation step for heating the polyester film after the heat fixing step, and reducing the length of the polyester film film transport direction and the direction orthogonal to the film transport direction, and In the heat relaxation step, the ratio of the length of the polyester film after the heat-fixing step to a direction orthogonal to the film transport direction is reduced, that is, a square orthogonal to the film transport direction. The relaxation rate on the film is set to 0.1% to 7%, and the relaxation rate in the film transport direction of the heat-fixed polyester film is set to 0.1% to 7% to form a film transport direction and be positive with respect to the film transport direction. A polyester film having a thermal shrinkage in the direction of intersection of 150 ° C. and a thermal history of 30 minutes was 3.0% or less.

The polyester film formation steps are as described in detail in the column of polyester film, and the preferred embodiment is also the same. In the manufacturing method of a decorative film, first, a polyester film is formed as a base material. The order of implementation of the subsequent steps, that is, the hard coat layer forming step and the decorative layer forming step, is arbitrary, and can be appropriately selected and implemented according to the configuration of the decorative film. Both the hard coating layer forming step and the decorative layer forming step can be performed first. In addition, in the case where the hard coating layer and the decorative layer are separately formed on both sides of the substrate including the polyester film, it can also be performed by multi-layer coating or simultaneous transfer. Printing method to form a hard coat layer and a decoration layer at the same time.

[Image Display Device] The image display device of the present disclosure includes an image display element and the decorative film of the present disclosure, and the decorative film is disposed on the outermost surface. Examples of the image display device of the present disclosure include image display devices such as a liquid crystal display device (Liquid Crystal Display (LCD)), a plasma display panel, an electroluminescence display, and a cathode tube display device.

Examples of the liquid crystal display device include a Twisted Nematic (TN) type, a Super-Twisted Nematic (STN) type, a Triple Super Twisted Nematic (TSTN) type, and a multi-domain (Multi domain) type, Vertical Alignment (VA) type, In Plane Switching (IPS) type, Optically Compensated Bend (OCB) type, etc. The image display device is particularly preferably a liquid crystal display device including a liquid crystal cell and the polarizing plate of the present disclosure arranged on at least one surface of the liquid crystal cell, and the decorative film of the present disclosure is arranged on the outermost surface. In this case, the image display element is a liquid crystal display element.

In the image display device of the present disclosure, the image display element is preferably an organic electroluminescence display element.

[Touch Panel] The touch panel of the present disclosure includes the decorative film of the present disclosure, and the decorative film is disposed on the outermost surface.

The touch panel to which the decorative film of the present disclosure can be applied is not particularly limited, and can be appropriately selected according to the purpose. For example, surface type capacitive touch panels, projection type capacitive touch panels, resistive film touch panels, and the like can be cited. The details will be described later as the resistive film touch panel of the present disclosure and the capacitive touch panel of the present disclosure. Furthermore, the so-called touch panel includes a so-called touch sensor and a touch pad. The layer structure of the touch panel sensor electrode part in the touch panel can be a bonding method in which two transparent electrodes are bonded, a method in which transparent electrodes are provided on both sides of a substrate, a single-sided jumper or a through-hole method. Or any of the single-area layer methods. In addition, with respect to a projection type electrostatic capacitive touch panel, an alternating current (AC) drive is better than a direct current (DC) drive, and a drive method with less time for applying voltage to the electrodes is more preferable.

(Resistance film type touch panel) The resistance film type touch panel of the present disclosure is a resistance film type touch panel including the decoration film of the present disclosure. The resistive film type touch panel includes a basic configuration in which conductive films of a pair of upper and lower substrates having a conductive film are disposed at positions facing each other with a spacer interposed therebetween. In addition, the configuration of the resistive film touch panel is well known, and the known technology can be applied without any limitation in the present disclosure.

(Capacitive Touch Panel) The capacitive touch panel of the present disclosure is a capacitive touch panel including the decorative film of the present disclosure. Examples of the method of the electrostatic capacitance type touch panel include a surface type electrostatic capacitance type and a projection type electrostatic capacitance type. A capacitive touch panel of a projection type includes a basic structure in which an X-axis electrode (hereinafter, also referred to as an X electrode) and a Y-axis electrode (hereinafter, also referred to as a Y electrode) orthogonal to the X electrode are arranged to isolate the edge body Make up. As a specific aspect, the X electrode and the Y electrode are formed on different surfaces of one substrate, and the X electrode, the insulator layer, and the Y electrode are sequentially formed on the one substrate. A state where an X electrode is formed on a substrate and a Y electrode is formed on another substrate (in this aspect, a structure in which two substrates are bonded together becomes the basic structure described above), and the like. Moreover, the configuration of the electrostatic capacitance type touch panel is well known, and the known technology can be applied without any limitation in the present disclosure. [Example]

Examples and comparative examples are given below to more specifically describe the decorative film and the like of the present disclosure. The materials, usage amounts, proportions, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present disclosure is not limitedly interpreted by the specific examples shown below. In addition, unless otherwise specified, "parts" and "ppm" are mass standards.

[Example 1] <Synthesis of raw material polyester> (raw material polyester 1) Raw material polyester 1 (Sb catalyst PET) was obtained by a continuous polymerization apparatus using a direct esterification method as shown below. In the direct esterification method, terephthalic acid and ethylene glycol are directly reacted, water is distilled off, and after esterification, polycondensation is performed under reduced pressure.

(1) Esterification reaction In the first esterification reaction tank, 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol were mixed for 90 minutes to form a slurry, and continuously supplied at a flow rate of 3800 kg / h Into the first esterification reaction tank. Further, an ethylene glycol solution of antimony trioxide was continuously supplied, and then the reaction was performed with stirring at a temperature in the reaction tank of 250 ° C. and an average residence time of about 4.3 hours. In the reaction, antimony trioxide was continuously added in an amount that the Sb addition amount became 150 ppm in terms of element conversion.

The obtained reactant was transferred to a second esterification reaction tank, and the reaction was performed with stirring at a temperature in the reaction tank of 250 ° C. and an average residence time of 1.2 hours. The amounts of Mg and P added were 65 ppm and 35 ppm, respectively, in terms of element conversion values. The ethylene glycol solution of magnesium acetate and the ethylene glycol solution of trimethyl phosphate were continuously supplied to the second esterification. Reaction tank.

(2) Polycondensation reaction The esterification reaction product obtained above is continuously supplied to the first polycondensation reaction tank, and the reaction temperature is 270 ° C and the pressure in the reaction tank is 20 torr (2.67 × 10 ^-3 MPa) under stirring. ), The average residence time is about 1.8 hours for polycondensation.

Further, it was transferred to a second polycondensation reaction tank, and in the second polycondensation reaction tank, under agitation, the temperature in the reaction tank was 276 ° C, the pressure in the reaction tank was 5 torr (6.67 × 10 ^-4 MPa), and it was retained. The reaction (polycondensation) was performed under conditions of about 1.2 hours.

Then, it was transferred to the third polycondensation reaction tank. In the third polycondensation reaction tank, the temperature in the reaction tank was 278 ° C, the pressure in the reaction tank was 1.5 torr (2.0 × 10 ^-4 MPa), and the residence time was 1.5 hours. The reaction (polycondensation) was carried out under the conditions described above to obtain a reactant (polyethylene terephthalate; PET).

Next, the obtained reactant was sprayed into cold water in a strand shape, and immediately cut to produce particles of polyester. "Section: major diameter: about 4 mm, minor diameter: about 2 mm, length: about 3" mm ".

The obtained polyester was IV = 0.63. The obtained polyester was used as a raw material polyester 1.

<Production of Polyester Film> -Film forming step- After drying the raw polyester 1 to a moisture content of 20 ppm or less, it is put into the hopper 1 of a uniaxial kneading extruder 1 having a diameter of 50 mm. The raw polyester 1 was melted to 300 ° C., and extruded from a mold through a gear pump and a filter (pore diameter: 20 μm) under the following extrusion conditions. The extrusion conditions of the molten resin were such that the pressure fluctuation was 1%, the temperature distribution of the molten resin was 2%, and the molten resin was extruded from the die. Specifically, a back pressure of 1% is applied to the average pressure in the barrel of the extruder, and the piping temperature of the extruder is heated to a temperature that is 2% higher than the average temperature in the barrel of the extruder. . The molten resin extruded from the mold was extruded onto a cooling casting drum set at a temperature of 25 ° C., and was brought into close contact with the cooling casting drum by an electrostatic application method. The peeling roll arrange | positioned opposite to the cooling casting drum was peeled, and the unstretched polyester film 1 was obtained.

—Formation of Easy Adhesive Layer— The following compounds were mixed at the following ratios to prepare a coating liquid H1 for easy adhesive layer formation.

(Coating Solution H1 for Easy Adhesive Layer Formation) Polyester resin: (IC) 60 parts by mass of acrylic resin: (II) 25 parts by mass of melamine compound: (VIB) 10 parts by mass of particles: (VII) 5 parts by mass of the following are shown Details of the compound used in the formation of the easy-adhesion layer are given.

-Polyester resin: (IC)-A sulfonic acid-based water dispersion monomer of a polyester resin obtained by copolymerizing monomers having the following composition: (acid component) terephthalic acid / isophthalic acid / Sodium isophthalate-5-sulfonate // (diol component) ethylene glycol / 1,4-butanediol / diethylene glycol = 56/40/4 // 70/20/10 (mole% )

-Acrylic resin: (II)-Aqueous dispersion of acrylic resin obtained by polymerizing monomers having the following composition: ethyl acrylate / n-butyl acrylate / methyl methacrylate / N-hydroxymethacrylamide / Emulsion polymer of acrylic acid = 65/21/10/2/2 (mass%) (emulsifier: anionic surfactant)

-Melamine compound: (VIB)-Hexamethoxymethyl melamine-Particles: (VII)-Silicone gel with an average particle diameter of 150 nm (The average particle diameter refers to the primary average particle diameter, that is, the average of the primary particle diameter; as described below The particle size is shown in the table).

-Coating of the easy-adhesive layer to both sides of the polyester film- The coating liquid H1 for forming the easy-adhesive layer was adjusted to be extended on one side of the unstretched polyester film 1 by a bar coating method using a wire rod. The subsequent coating film thickness was an amount of 50 nm, and coating was performed using wire rod coating.

-Horizontal Stretching Step- The unstretched polyester film 1 is introduced into a tenter (horizontal stretching machine), and while the end portion of the film is held by a jig, it is stretched horizontally in the following method and conditions.

(Preheating section) Heating is performed by hot air so that the surface temperature at the extension start point becomes 89 ° C. In addition, the surface temperature at the extension start point is the position at the center of the film width direction with a radiation thermometer (manufactured by Lin Dian, model: RT61-2, used at an emissivity of 0.95) at the point where the extension started. Measured.

(Extended portion) While the preheated unstretched polyester film 1 is heated by hot air, it is laterally stretched in the width direction (TD) using a tenter under the following conditions. In addition, the surface temperature at each extension magnification time point is measured at the central portion in the width direction of the film by a radiation thermometer (manufactured by Lin Dian, model: RT61-2, used at an emissivity of 0.95) at each extension magnification time point. The position is determined by measurement.

<Conditions> · Horizontal extension magnification: 4.1 times · Surface temperature at 2 times extension time: 90 ° C · Surface temperature at 3 times extension time: 94 ° C · Surface temperature at extension end time: 95 ° C

(Heat Fixing Step) Then, the hot air is blown out of the nozzle, and hot air from the film is blown up and down on the film, and the surface temperature of the polyester film is controlled to the following range, and heat fixing is performed. <Conditions> · Maximum reached surface temperature (heat-fixed temperature): 168 ° C

(Heat easing step) In the heat easing step, easing by the tenter stretcher and easing of adjusting the transfer speed and the gripper interval during the transfer are performed by the method shown in Table 1 or Table 2 below. The relaxation rate shown in the following Table 1 or Table 2. The relaxation conveying tension in the heat relaxation step, the polyester film film surface temperature at the time of heat relaxation (referred to as "relaxation film surface temperature" in Tables 1 and 2), and the processing time at the time of heat relaxation (in Tables 1 and 2) It is described as "relaxation processing time"), and the cooling rate when the film surface temperature in the range of 70 ° C ± 20 ° C during cooling after thermal relaxation (described as "relaxation cooling rate" in Tables 1 and 2) is shown in Table 1 respectively. Or in Table 2.

(Cooling Section) Next, the cooling air is blown onto the film by blowing out the nozzle from the cold air, and cooling is performed on the film. Cooling was performed so that the surface temperature when the clamp of the film self-tenter was released became 40 ° C. The film surface temperature was obtained by measuring the position of the central portion in the width direction of the film with a radiation thermometer (manufactured by Lin Dian, model: RT61-2, used at an emissivity of 0.95).

(Recycling of the film) After cooling and releasing the film from the jig, trim both ends of the polyester film by 20 cm. The trimmed film width was 2 m. After that, both ends were extruded (rolled) with a width of 10 mm, and then a film with a length of 10,000 m was wound into a roll shape with a tension of 18 kg / m. As described above, the polyester film 1 of Example 1 having a thickness of 150 μm wound in a roll form and used for the production of a decorative film was produced.

[Film Measurement Results] The obtained polyester film 1 was measured for the following physical properties. The measurement results are shown in Table 1 or Table 2 below.

<Thickness> The thickness of the obtained polyester film 1 was calculated | required as follows. For the polyester films of each of the Examples and Comparative Examples, a contact-type film thickness meter (manufactured by Anritsu) was used, and samples were sampled at equal intervals across a length of 0.5 m in the longitudinally extending direction (lengthwise direction) 50. After 50 samples were taken across the entire width of the film in the film width direction (direction orthogonal to the length direction) at equal intervals (50 equal divisions in the width direction), the thickness at the 100 points was measured. The average thickness at the 100 points was determined and set as the thickness of the polyester film.

<Re, Rth, Re / Rth ratio> Re and Rth were calculated | required by the method mentioned above about the film obtained by each Example and the comparative example. The Re / Rth ratio was calculated from the obtained Re and Rth.

<Thermal shrinkage rate> The polyester film was cut into a width of 30 mm and a length of 120 mm for the MD direction and the TD direction to obtain a sample piece M of the polyester film, and the thickness of the polyester film was 100 mm in the longitudinal direction. Way into 2 baselines. After leaving the sample piece M in a heating oven at 150 ° C. for 30 minutes under no tension, the sample piece M was cooled to room temperature, and the interval between the two reference lines was measured. The measured heat treatment interval is set to A [mm], and is calculated from the 100 mm interval before the treatment and the A mm interval after the treatment using the formula "100 × (100-A) / 100" The value [%] is set to the thermal shrinkage rate of the sample piece M (150 ° C, 30 minutes). In the measurement, three specimens were measured at three locations in each direction, and the arithmetic average of the measurement results at a total of nine locations was set as the measurement value. The results are shown in Table 1 or Table 2.

[Formation of Hard Coating Layer] A hard coating layer forming composition 1 having the following composition was prepared. (Composition of composition 1 for hard coat layer formation) · 3,4-epoxycyclohexyl methyl acrylate [a] component] 40 parts by mass · DPHA: KAYARAD DPHA (Nippon Kayaku Co., Ltd.) (Manufacturing) [b] Ingredients] 55.4 parts by mass · Irgacure 127: Alkyl phenone-based photopolymerization initiator (BASF (manufactured)) [c] Ingredients] 2.0 parts by mass · Yanacure (Irgacure) 290: phosphonium salt-based cationic polymerization initiator (BASF (manufactured)) [d] Component] 2.0 parts by mass · FP-1: Fluorine compound of the following structure [Anti-wind unevenness agent] 0.10 mass Parts · Solvent: 200 parts by mass of methyl ethyl ketone (MEK) · Solvent: 100 parts by mass of methyl isobutyl ketone (MIBK)

[Chemical 14]

The application of the coating liquid for forming a hard coat layer was performed by the following method. The uniaxially stretched polyester film used in Example 1 which was wound into a roll form was rolled out, and as a subsequent step, the coating solution for forming a hard coat layer described above was applied by the following method. For the hard coat layer, an easy-adhesion layer is provided on one side of the film, and the side where the easy-adhesion layer is formed is subjected to a die coating method using a slit die as described in Example 1 of Japanese Patent Laid-Open No. 2006-122889. The coating liquid for forming a hard coat layer was applied at a conveying speed of 30 m / min, and dried in a drying area at a temperature of 60 ° C. for 150 seconds. After that, it is conveyed to a hardening area to harden the composition for hard-coat layer formation. In the hardened area, the oxygen concentration was adjusted to about 0.1% under a nitrogen purge. An air-cooled metal halide lamp (manufactured by Eyegraphics (Stock)) was used at 160 W / cm, and the illumination intensity was 400 mW / cm ² . The hard coat layer was hardened by irradiating 500 mJ / cm ² of ultraviolet rays, and the laminated body having the hard coat layer formed on the film was taken up. In addition, in other Examples and Comparative Examples, the base film described in Tables 1 and 2 was used to form a hard coat layer in the same manner. When an easy-adhesion layer is not provided, a hard-coat layer is formed on any one surface of the film | membrane which is a base material.

<Film thickness of the hard coat layer> The film thickness of the hard coat layer is measured by a contact-type film thickness meter, and the polyester film measured in the same manner is subtracted from the film thickness of the produced hard coat layer. Thickness. The results are shown in Table 1 or Table 2.

[Formation of decorative layer] (1. Production of decorative film for forming decorative layer) <Preparation of composition for forming decorative layer> A composition for forming a decorative layer 1 (colored composition) was obtained in the following procedure. (Composition of composition 1 for forming a decorative layer) • The following K pigment dispersant (the following composition) 137.4 parts by mass • Dipentaerythritol (penta / hexa) acrylate [polymerizable compound] (Nippon Kayaku Co., Ltd., Card KAYARAD (DPHA) 19.5 parts by mass · tricyclodecanediol dimethanol diacrylate [Polymerizable compound] (Shinakamura Chemical Industry Co., Ltd., A-DCP) 6.5 parts by mass · Cyclomethacrylate Glycidyl methacrylate adduct (a) / methyl methacrylate (b) / methacrylic acid copolymer (c) (d), a / b / c / d = 46/1/10 / 43, weight-average molecular weight: 36000) 1-methoxypropanol methyl ethyl ketone solution (solid content: 45% by mass) [binder] 81.2 parts by mass · 1,2-octanedione-1- [4 -(Phenylthio) -2- (O-benzylideneoxime)] [Polymerization initiator] (Trade name: IRGACURE OXE-01, manufactured by BASF) 9.2 parts by mass of brown Thiazine [polymerization inhibitor] 0.3 parts by mass · The following structure 1 [ Surface active agent] 0.4 parts by mass 1-Methoxy-2-propyl acetate [solvent] 238.7 parts by mass Methyl ethyl ketone (of MEK) [Solvent] 321.3 parts by mass

[Chemical 15]

(K pigment dispersion 1) · Resin-coated carbon black prepared according to Japanese Patent No. 5320625 <0036> to <0042> 13.1% by mass · The following dispersant 1 0.65% by mass · Polymer 6.72% by mass (methacrylic acid Random copolymer of benzyl ester / methacrylic acid = 72/28 mole ratio, weight average molecular weight 37,000) · Propylene glycol monomethyl ether acetate 79.53% by mass

[Chemical 16]

First, the K pigment dispersion 1 in an amount described in the composition of the decorative layer-forming composition 1 was weighed out, mixed at a temperature of 24 ° C. (± 2 ° C.), and subjected to 150 revolutions per minute (Round Per Minutes, RPM). ) Stir for 10 minutes to obtain solution 1. Next, weigh out methyl ethyl ketone, 1-methoxy-2-propyl acetate, adhesive, phenothiazine, polymerizable compound, polymerization initiator, and surfactant at a temperature of 25 ° C (± 2 ° C) was added to the solution 1 obtained above in the order described, and the mixture was stirred at 150 RPM for 30 minutes at a temperature of 24 ° C (± 2 ° C).

<Preparation of Transfer Film> A coating liquid for a thermoplastic resin layer containing the following formula H1 was applied to a 75 μm-thick polyethylene terephthalate film temporary support and dried using a slit nozzle. . Next, a coating liquid for an intermediate layer containing the following formula P1 is applied and dried. After that, the aforementioned decorative layer-forming composition 1 is applied and dried. A thermoplastic resin layer having a dry film thickness of 15.1 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a composition layer for forming a black decorative layer having a dry film thickness of 2.0 μm were provided on the temporary support in the manner described above. Protective film (12 μm thick polypropylene film). In this way, a transfer film in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen blocking film), the composition layer for forming a black (K) decorative layer, and the protective film are integrated is prepared.

(Coating solution for thermoplastic resin layer: Formulation H1) · 11.1 parts by mass of methanol · 6.36 parts by mass of propylene glycol monomethyl ether acetate · 52.4 parts by mass of methyl ethyl ketone · Methyl methacrylate / acrylic acid-2-ethyl Hexyl ester / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ° C) 5.83 parts by mass · styrene / Acrylic copolymer (composition ratio (mole ratio) = 63/37, weight average molecular weight = 10,000, Tg ≒ 100 ° C) 13.6 parts by mass · 2,2-bis [4- (methacrylic acid 醯 oxypoly Ethoxy) phenyl] propane (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) 9.1 parts by mass · 0.54 parts by mass of a fluoropolymer (40 parts of C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ and 55 parts of H (OCH (CH ₃ ) CH ₂ ) 7OCOCH = CH ₂ and 5 parts of H (OCH ₂ CH ₂ ) ₇ OCOCH = CH ₂ copolymer, weight average molecular weight 30,000, methyl ethyl ketone 30% by mass solution, Di (Manufactured by DIC, trade name: Megafac F780F)

(Coating solution for intermediate layer: Formula P1) · 32.2 parts by mass of PVA205 (manufactured by polyvinyl alcohol, Kuraray (shares), degree of saponification = 88%, degree of polymerization 550) · polyvinylpyrrolidone 14.9 Parts by mass (manufactured by Japan ISP, K-30) • 524 parts by mass of distilled water • 429 parts by mass of methanol

(2. Formation of Decorative Layer by Transferring and Patterning) <Transferring> On the surface of the polyester film 1 having the easy-adhesion layer on the side where the hard coat layer is not formed, it is removed from the obtained transfer film The protective film was superimposed in a direction in which the surface of the black decorative layer-forming composition layer and the surface of the polyester film 1 that were exposed after removal were overlapped, and a laminator (manufactured by Hitachi Industries, Ltd. (Lamic) Type II)). Laminating was performed at a rubber roller temperature of 130 ° C, a linear pressure of 100 N / cm, and a conveying speed of 2.2 m / min. Then, the temporary support of polyethylene terephthalate was peeled off at the interface with the thermoplastic resin layer to remove the temporary support.

<Patternization of decorative layer> After peeling off the temporary support, a proximity exposure machine (made by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp was used to make the substrate Set the distance between the exposure mask surface and the black composition layer-forming composition layer in a state of standing upright to the mask (a quartz exposure mask having an image pattern remaining only on the peripheral edge portion of the polyester film) It was 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² . Next, the triethanolamine-based developer (containing 30% by mass of triethanolamine, and the product name: T-PD2 (manufactured by Fujifilm) was diluted 12 times with pure water (with 1 part of T-PD2 and 11 parts of pure water). The liquid was mixed at a ratio of 5%) at 30 ° C, and was subjected to spray development at a flat nozzle pressure of 0.1 MPa for 20 seconds to remove the thermoplastic resin layer and the intermediate layer. Next, air is blown onto the upper surface of the polyester film 1 to perform liquid drainage, and then pure water is sprayed and sprayed for 10 seconds to perform pure water spray cleaning, and air is blown to reduce liquid accumulation on the substrate.

Thereafter, a sodium carbonate / sodium bicarbonate-based developer solution (brand name: T-CD1 (manufactured by Fujifilm Corporation) was diluted to 5 times with pure water (at a ratio of 1 part of T-CD1 to 4 parts of pure water). A liquid obtained by mixing), the spray pressure was set to 0.1 MPa at 30 ° C., and the composition layer for forming a decorative layer was developed for 30 seconds and washed with pure water.

Next, a surfactant-containing cleaning solution (a liquid obtained by diluting the trade name: T-SD3 (manufactured by Fujifilm) with pure water 10 times with pure water) was used, and the cone nozzle pressure was 0.1 at 33 ° C. The MPa was blown by spraying for 20 seconds to wash the composition layer for forming a decorative layer. Furthermore, the ultra-high pressure cleaning nozzle was used to spray ultrapure water at a pressure of 9.8 MPa to remove the residue. In this way, the decorative film of Example 1 in which the composition layer for forming a decorative layer was formed on the peripheral edge portion of the surface on the side where the hard coat layer was not formed was obtained.

[Evaluation] The following evaluation was performed on the decorative film obtained in Example 1. The evaluation results are shown in Table 1 or Table 2 below.

<Curl value> The decorative film was cut into a length of 50 mm and a width of 50 mm to produce a decorative film sheet as a test piece. Put it into a heating furnace at a temperature of 150 ° C for 30 minutes. After that, remove the decorative film and cool it to room temperature, place it on a flat surface, and measure the distance between the flat surface and the measurement target part in the decorative film. The distance, that is, the amount of warpage of the decorative film is taken as the curl value (H). A total of 8 corners were formed at the four corners of the test piece whose measurement target site was a square, and the central part of one side of the four squares. The curl value is the average value of the curl values measured at the eight measurement target sites described above, and the average value of the curl values measured for the five test pieces is calculated as the curl shown in Table 1 or Table 2. value. When the decorative film is curled into a convex shape with respect to a flat place after heating, the decorative film is inverted and arranged in a concave shape to measure the curl value. The results are shown in Table 1 or Table 2 below.

<Stamp Evaluation> The decorative film was subjected to 10 punching processes, and chipping of the hard coating layer on the punched end surface, peeling state of the decorative layer and base material, and peeling state of the base material and hard coating layer were evaluated based on the following criteria. A: No chipping / peeling at all B: One chipping / peeling occurred C: Two chipping / peeling D: Three chipping / peeling

<Surface Abrasion Resistance Evaluation> The pencil hardness of the surface of the decorative film (the side having the hard coat layer) was measured according to the method described in JIS K-5600 5-4. When the pencil hardness is H or more, it is evaluated that it has practically sufficient surface abrasion resistance. A: Pencil hardness is 5H or more B: Pencil hardness is 3H ～ 4H C: Pencil hardness is H ～ 2H D: Pencil hardness is less than H

<Evaluation of visibility> The hard coating film is sandwiched between polarizing plates provided at the cross-Nicols so that the alignment angle of the hard coating film is inclined by 45 ° with respect to the absorption axis of the polarizing plate, and the LED backlight is illuminated from the rear. The visibility was evaluated by the following criteria. A: No rainbow-like unevenness is seen at all B: Rainbow-like unevenness is hardly seen C: Rainbow-like unevenness is slightly seen, but tolerable D: Rainbow-like unevenness is clearly seen

[Example 2 to Example 16, Comparative Example 1 to Comparative Example 6] In Example 1, the thickness of the polyester film used in the substrate, and the length of the stretching step were changed as described in Table 1 or Table 2 below, respectively. Except for the conditions, the presence or absence of an easy-to-adhere layer, the presence or absence of a hard coat layer, and the composition of the hard coat layer, the decorative films of Examples and Comparative Examples were produced in the same manner as in Example 1. In Example 16, instead of the uniaxially stretched polyester film, a biaxially stretched polyester film manufactured under the following conditions was used as a substrate. In Comparative Examples 1 to 4, the following was used instead of the polyester film. Shown resin substrate.

The details of the base film used in Example 16 and Comparative Examples 1 to 4 are as follows. -Biaxially stretched PET- In the polyester film used in Example 1, a biaxially stretched polyester film stretched in the MD direction in addition to the stretch in the TD direction at a magnification of 3.2 times was obtained as a base material. membrane. -PC- Polycarbonate (PC) film: Sumika Acrylic Sales (stock), Technolloy C1000 (trade name), thickness 150 μm -PMMA- Polymethyl methacrylate (PMMA) film: Sumika Acrylic acid sales (shares), Technolloy S1000 (trade name), thickness 150 μm -PMMA / PC / PMMA- film laminated in the order of PMMA / PC / PMMA, Sumika acrylic acid sales (shares), Technolloy C-101 (trade name), thickness 300 μm

The formulation of the hard coat layer-forming composition 2 used in Examples 15 to 17 is as follows. (Composition of composition 2 for forming a hard coat layer: used in Example 15) · 3,4-epoxycyclohexyl methyl acrylate [a] component] 39 parts by mass · DPHA: KAYARAD DPHA ( (Manufactured by Nippon Kayaku Co., Ltd.) [b] Ingredients] 55.4 parts by mass · Irgacure 127: Alkyl phenone-based photopolymerization initiator (BASF (manufactured)) [c] Ingredients] 2.5 Parts by mass · Irgacure 290: phosphonium salt-based cationic polymerization initiator (BASF (manufactured)) [d] Ingredient] 2.0 parts by mass · FP-1 [Wind-induced unevenness preventive agent] 0.10 parts by mass · RS-90: (Brand name, DIC (shares)) [Antifouling agent] 1.0 parts by mass · Solvent: MEK 200 parts by mass · Solvent: MIBK 100 parts by mass

(Composition of composition 3 for hard coat layer formation: used in Examples 16 to 17) · 3,4-epoxycyclohexyl methyl acrylate [a] component] 12.0 parts by mass · DPHA: Kayalade ( KAYARAD) DPHA (manufactured by Nippon Kayaku Co., Ltd.) [b] Ingredients] 83.0 parts by mass · Irgacure 127: alkyl phenone-based photopolymerization initiator (BASF (manufactured)) [c Ingredients] 3.7 parts by mass · Irgacure 290: phosphonium salt-based cationic polymerization initiator (BASF (manufactured)) [d] Ingredients] 1.2 parts by mass · FP-1 [Wind-induced unevenness prevention agent ] 0.10 parts by mass · Solvent: 200 parts by mass of MEK · Solvent: 100 parts by mass of MIBK

[Table 1]

[Table 2]

From the evaluation results described in Tables 1 and 2, it can be seen that compared with the decorative film of the comparative example, the decorative film of the example having a curl value of 5 mm or less after a thermal history at 150 ° C and 30 minutes, and a heat shrinkage The decorative film of the example in which the polyester film with a rate (150 ° C, 30 minutes) of 3.0% or less was used as the base material had good abrasion resistance, and cracks, chippings, and peeling between layers during stamping were all generated. Get suppressed. Among these, by using a uniaxially stretched polyester film as a substrate, in addition to the effects of the present invention, the visibility of the decorative film is further improved.

10‧‧‧Decorative film (decorative film)
12‧‧‧ flat
13‧‧‧Jig (holding member)
14‧‧‧Decorative layer
16‧‧‧ Substrate including polyester film
18‧‧‧hard coating
20‧‧‧ decorative film
22‧‧‧decorative film
H‧‧‧ Arrow

FIG. 1A is a schematic diagram showing details of a curl value measurement method of a decorative film, and is a plan view of a curl film value measurement decorative film sheet. FIG. 1B is a schematic view showing the details of the curl value measurement method of the decorative film, and is a schematic side view showing the state of the decorative film sheet during the curl value measurement. FIG. 1C is a schematic view showing the details of the curl value measurement method of the decorative film, and is a schematic side view showing a state of the rolled decorative film that needs to be reversed. FIG. 2 is a partial schematic view showing an example of a configuration of a tenter stretching device used in a lateral stretching step. FIG. 3 is a plan view showing an embodiment of the decorative film. FIG. 4A is a schematic side view showing an example of a modification of the layer configuration of the decorative film. FIG. 4B is a schematic side view showing an example of a modification of the layer configuration of the decorative film. 4C is a schematic side view showing an example of a modification of the layer configuration of the decorative film. 5A is a schematic cross-sectional view showing an example of a modification example of the layer configuration of the decorative film. 5B is a schematic cross-sectional view showing an example of a modification of the layer configuration of the decorative film.

no

Claims (20)

A decorative film comprising a polyester film, a decorative layer, and a hard coat layer, which is generated when a 50 mm length and 50 mm width film is given a thermal history at a temperature of 150 ° C for 30 minutes to a film of the decoration film. The curl value of the decorative film is 5 mm or less. The decorative film according to item 1 of the patent application scope, wherein the decorative layer has the decorative layer in at least a part of the entire area of the decorative film in a plan view. The decorative film according to item 1 or item 2 of the patent application range, wherein the in-plane retardation Re of the polyester film at a measurement wavelength of 589 nm is in a range of 3000 nm to 50000 nm. A decorative film comprising a polyester film, a decorative layer, and a hard coat layer. When the polyester film is given a thermal history of 150 ° C. and 30 minutes, a direction in the plane of the polyester film and the same The thermal contraction rate in the directions orthogonal to each other in the plane was 3.0% or less. The decorative film according to item 4 of the scope of patent application, wherein the polyester film is a uniaxially oriented polyester film. The decorative film according to item 4 or 5 of the scope of application for a patent, wherein the decorative layer is disposed on one side of the polyester film, and the hard coating layer is disposed on the polyester film. The surface of the decorative layer is a surface on the opposite side. The decorative film according to claim 4 or 5, wherein the decorative film has the decorative layer in at least a part of the entire area of the decorative film in a plan view. The decorative film according to item 4 or item 5 of the scope of patent application, wherein the thickness of the polyester film is 40 μm to 500 μm. The decorative film according to item 4 or item 5 of the patent application scope, wherein the in-plane retardation Re of the polyester film at a measurement wavelength of 589 nm is in a range of 3000 nm to 50000 nm. The decorative film according to item 4 or item 5 of the patent application scope, wherein the in-plane retardation Re of the polyester film at a measurement wavelength of 589 nm is relative to the thickness direction of the polyester film at a measurement wavelength of 589 nm The ratio of the retardation Rth is in the range of 0.6 to 1.2. The decorative film according to item 4 or item 5 of the scope of patent application, which has an easy-adhesion layer on at least one side of the polyester film. The decorative film according to item 4 or item 5 of the scope of patent application, wherein the pencil hardness of the hard coating layer is H or more. The decorative film according to item 4 or item 5 of the scope of patent application, wherein the thickness of the hard coating layer is 5 μm or more. The decorative film according to claim 4 or 5, wherein the hard coating layer includes at least a structure derived from a) below, a structure derived from b) below, c) below, and d) and a structure derived from the following a) and a structure derived from the following b) of 15% to 70% by mass with respect to the total solid content of the hard coat layer 0.1 to 10% by mass of the following c), 0.1 to 10% by mass of the following d); a) having an alicyclic epoxy group and an ethylenically unsaturated double bond in the molecule A compound having a molecular weight of 300 or less, b) a compound having three or more groups containing an ethylenically unsaturated double bond in the molecule, c) a radical polymerization initiator, and d) a cationic polymerization initiator. An image display device includes an image display element and the decorative film according to any one of claims 1 to 14 of the scope of patent application, and the decorative film is provided on the outermost surface. A touch panel includes the decorative film according to any one of items 1 to 14 of the scope of patent application, and is provided with the decorative film on the outermost surface. A method for manufacturing a decorative film, comprising: a polyester film forming step; a decorative layer forming step for forming a decorative layer on at least a part of one side of the polyester film; and a hard coat layer forming step for the polyester A hard coat layer is formed on at least one side of the film, and the polyester film forming step includes a lateral stretching step using a tenter having a plurality of clamps that move along a pair of rails provided on both sides of the film conveying road, respectively. A type stretching device, in a state in which an unstretched polyester film is held by the jig, the stretching is performed in a direction orthogonal to the film conveying road; the heat fixing step is performed after Heating the polyester film for heat fixing; and a heat relaxation step for heating the polyester film after the heat fixing step, and reducing the film conveying direction of the polyester film and orthogonal to the film conveying direction Length of the direction, and in the heat relaxation step, the relaxation rate in the film conveying direction of the polyester film after the heat fixing step is set to 0.1% to 7%, and is positive relative to the film conveying direction. Pay party The upward relaxation rate is set to 0.1% to 7%, and the thermal contraction rate at the time of forming a film transport direction and a direction orthogonal to the film transport direction at a temperature of 150 ° C for 30 minutes is 3.0%. The following polyester film. The method for manufacturing a decorative film according to item 17 of the scope of patent application, wherein the length of the polyester film in the thermal relaxation step in a direction orthogonal to the film transport direction includes reducing the length of the polyester film provided in the film transport. The distance between a pair of tracks on both sides of the road, and the shrinking the length of the film transport direction of the polyester film in the thermal relaxation step includes reducing the interval between the plurality of moving clamps. The method for manufacturing a decorative film according to claim 17 or claim 18, wherein the reducing the length of the film conveying direction of the polyester film in the heat relaxation step includes applying tension in the film conveying direction of the polyester film And under heating conditions, the length is reduced while being conveyed. The method for manufacturing a decorative film according to item 17 or 18 of the scope of application for a patent, wherein the conveying tension of the polyester film in the heat relaxation step is 10 N / m width to 80 N / m width, and the polyester film The film surface temperature during heating is 110 ° C to 190 ° C, and the heat treatment time is 10 seconds to 600 seconds. When the length of the polyester film is reduced after cooling, the film surface temperature of the polyester film is 70. The cooling rate in the range of ℃ ± 20 ° C is 100 ° C / min to 2000 ° C / min.