TWI746514B - Decorative film, image displaydevice, touch panel, and method of producing decorative film - Google Patents

Abstract

A decorative film, its application, and a manufacturing method thereof. The decorative film has a polyester film, a decorative layer and a hard coat layer, and is applied to a decorative film with a length of 50 mm and a width of 50 mm at a temperature of 150°C for 30 minutes. The curl value of the decorative film produced during the process is less than 5 mm.

Description

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

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

Cathode tube display device, plasma display (plasma display), electroluminescence display (electroluminescence display), fluorescent display display, field emission 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 smart phones and tablet terminals equipped with touch panels, hard coating is provided on a support containing resin as the main component Layer and laminated film with decorative layer.

The hard coat layer is usually provided for the purpose of preventing damage to the image display surface. The laminated film having the decorative layer is arranged for the purpose of hiding wiring arranged in the device body on the image display surface and applying various designs.

Especially, in small terminals equipped with touch panels, you will directly touch with your fingers. Or use a stylus to touch the screen, so in order to effectively prevent damage to the film, the image display surface is required to have good abrasion resistance.

When the hardness of the hard coat layer is increased to make a hard film, when the decorative film with the hard coat layer and the decorative layer is processed and fixed on the display, the size of the decorative film is adjusted by pressing. Make adjustments. Polyester film substrate, hard hard coat and decorative layers containing decorative coloring agents that have different physical properties from the hard coat have different mechanical strength, elongation, etc., so interlayer peeling may occur during press processing Or cracks occur in the hard hard coating.

For example, as a hard coat film for an image display surface that has moderate surface hardness and can be used in combination with a decorative layer, a hard coat film having an acrylic resin substrate and having specific physical properties has been proposed (for example, refer to Japanese Patent Laid-Open Bulletin No. 2014-109712).

In addition, a cover film for the image display surface has been proposed which 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 of is covered by a hard coat, 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 having a resin layer containing particles and having a specific haze value and Martens hardness (Martens hardness) is proposed, and it is described that it imparts a good touch to the surface (for example, refer to Japanese Patent Laid-Open No. 2013- Bulletin No. 244624).

However, according to research conducted by the inventors of the present invention, in a decorative film having a resin base material, a decorative layer, and a hard coat layer, the physical properties of the various constituent elements are greatly different, so Various problems arise.

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 adjacent decorative layer and the resin substrate may deteriorate. reduce. Furthermore, due to the physical properties under the thermal history, when the decorative film is pressed into an appropriate shape, interlayer peeling between the hard coat layer and the resin substrate or decorative layer may occur, or cracks may occur during the pressing process Or chipped. Furthermore, in Japanese Patent Laid-Open No. 2014-109712, as a comparative example, it is disclosed that a polyethylene terephthalate substrate is used instead of an acrylic resin substrate, but it is described when the image is displayed Rainbow-like unevenness and blackout caused by the phase difference of incident light will occur. That is, it is considered that a hard coat film using a polyethylene terephthalate substrate has a problem in optical properties. Therefore, in the technique described in Japanese Patent Laid-Open No. 2014-109712, the use of a polyester film is not considered于The substrate.

In addition, in the cover film described in Japanese Patent Application Laid-Open No. 2014-35493, the area that does not have the decorative layer is covered by the hard coat layer, so the adhesion between the hard coat layer and the decorative layer is improved. However, similar to the film described in Japanese Patent Laid-Open No. 2014-109712, the cover film described in Japanese Patent Laid-Open No. 2014-35493 has the resin substrate and the hard coat layer undergoing heat. In the case of the history, the physical properties may cause delamination between the hard coat layer and the resin substrate, or cracks or chipping may occur during press processing.

The coating material for a frame described in Japanese Patent Laid-Open No. 2013-244624 is based on the premise that inline coating is used when covering the surface of the frame. It is not envisaged to perform press processing to make the size uniform when installed in the frame. Since the coating material described in JP 2013-244624 A has a resin layer containing particles, it has a soft touch when touched with a finger. However, as described above, press processing and the like are not envisaged. However, even if press processing is performed, the resin layer contains particles, which results in low press processing adaptability and may cause cracks during press processing.

The problem of one embodiment of the present invention is to provide a decorative film, an image display device and a touch panel provided with the decorative film, which suppress the occurrence of cracks and chipping during press processing and are excellent in scratch resistance.

In addition, the subject of another embodiment of the present invention is to provide a method of manufacturing a decorative film that can produce a decorative film that suppresses the occurrence of chipping during press processing and is excellent in scratch resistance.

This disclosure includes the following embodiments.

<1> A decorative film, which has a polyester film, a decorative layer, and a hard coat layer. The decorative film is produced when a thermal history of 150°C for 30 minutes is applied to a film with a length of 50 mm and a width of 50 mm. The curl value is 5mm or less.

<2> The decorative film according to <1>, which 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 as described in <1> or <2>, wherein the in-plane retardation Re of the polyester film at a measurement wavelength of 589 nm is in the range of 3000 nm to 50000 nm.

<4> A decorative film, which has a polyester film, a decorative layer, and a hard coat layer. When a thermal history of 150°C for 30 minutes is applied to the polyester film, the surface of the polyester film The thermal shrinkage rate in one direction of and in the direction orthogonal to the one direction in the plane is 3.0% or less.

<5> The decorative film as described in <4>, wherein the polyester film is a uniaxially aligned polyester film.

<6> The decorative film as described in <4> or <5>, wherein the decorative layer is arranged on one side of the polyester film, and the hard coat layer is arranged on the opposite side of the polyester film and the surface on which the decorative layer is arranged noodle.

<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 the 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 relative to the thickness direction retardation of the polyester film at a measurement wavelength of 589 nm The ratio of 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 pencil hardness of the hard coat layer is H or higher.

<13> The decorative film according to any one of <4> to <12>, wherein the hard coating The thickness of the 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 the structure derived from the following a), the structure derived from the following b), the following c), and The following d), with respect to the total solid content of the hard coat layer, contains 15% to 70% by mass of the structure derived from the following a), and 25% to 80% by mass of the structure derived from the following b) , 0.1% by mass to 10% by mass in the following c), 0.1% by mass to 10% by mass in the following d);

a) A compound with an alicyclic epoxy group and a group containing an ethylenically unsaturated double bond in the molecule, and the molecular weight is less than 300

b) Compounds having three or more groups containing ethylenically unsaturated double bonds in the molecule

c) Free radical polymerization initiator

d) Cationic polymerization initiator.

<15> An image display device comprising an image display element and the decorative film according to any one of <1> to <14>, and the decorative film is provided on the outermost surface.

<16> A touch panel, comprising the decorative film as described in any one of <1> to <14>, and having the decorative film on the outermost surface.

<17> A method for manufacturing a decorative film, comprising: a step of forming a polyester film; a step of forming a decorative layer, forming a decorative layer on at least a part of one side of the polyester film; and a step of forming a hard coat layer on the polyester film. A hard coat layer is formed on at least one surface of the film, and the polyester film forming step includes a lateral stretching step using a plurality of jigs that move along a pair of rails provided on both sides of the film conveying road. The tenter-type stretching device stretches the unstretched polyester film in a state in which the unstretched polyester film is clamped by a clamp, and stretches in a direction orthogonal to the film conveying path; the heat-fixing step involves The film is heated for heat fixation; and the heat relaxation step is to heat the polyester film after the heat fixation step, and reduce the length of the film transport direction of the polyester film and the direction perpendicular 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 fixation step is set to 0.1% to 7%, and the relaxation rate in the direction orthogonal to the film transport direction is set to 0.1% ~7%, to form a polyester film with a heat shrinkage rate of 3.0% or less in the film conveying direction and the direction orthogonal to the film conveying direction at a temperature of 150°C and a heat history of 30 minutes.

<18> The method of manufacturing a decorative film according to <17>, wherein the shrinking of the length of the polyester film in the direction perpendicular to the film conveying direction in the heat relaxation step includes shrinking and installing on both sides of the film conveying path The distance between the pair of rails, the reduction of the length of the polyester film in the film transport direction in the heat relaxation step includes the reduction of the distance between the moving clamps.

<19> The method for manufacturing a decorative film as described in <17> or <18>, wherein the shrinking of the length of the polyester film in the film transport direction in the heat relaxation step includes applying tension in the film transport direction of the polyester film to The length is reduced while conveying under the heating condition.

<20> The manufacturing method of the decorative film as described in any one of <17> to <19>, 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℃~190℃, and the heat The processing time is from 10 seconds to 600 seconds. When cooling after reducing the length of the polyester film, the cooling rate when the film surface temperature of the polyester film is in the range of 70℃±20℃ is 100℃/min~2000℃/ min.

According to an embodiment of the present invention, it is possible to provide a decorative film, an image display device including the decorative film, and a touch panel in which the occurrence of chipping during press processing is suppressed and the scratch resistance is excellent.

In addition, according to another embodiment of the present invention, it is possible to provide a method of manufacturing a decorative film, which can produce a decorative film that suppresses the occurrence of chipping during press processing and is excellent in scratch resistance.

10: Decorative film (decorative film)

12: Flat

13: Clamp (clamping member)

14: Decorative layer

16: Substrate including polyester film

18: Hard coating

20: Decorative film

22: Decorative film

H: Arrow

100: Warm-up step

200: Horizontal extension step

300: heat fixation step

400: heat mitigation steps

FIG. 1A is a schematic diagram showing the details of the method for measuring the curl value of a decorative film, and is a plan view of a decorative film sheet for measuring the curl value.

1B is a schematic diagram showing the details of the method of measuring the curl value of the decorative film, and is a schematic side view showing the state of the decorative film sheet in the curl value measurement.

FIG. 1C is a schematic diagram showing the details of the method for measuring the curl value of the decorative film, and is a schematic side view showing the state of the curled decorative film that needs to be turned over.

Fig. 2 is a partial schematic view showing an example of the configuration of a tenter stretching device used in a lateral stretching step.

Fig. 3 is a plan view showing an embodiment of a decorative film.

4A is a schematic side view showing an example of a modification of the layer structure of the decorative film.

4B is a schematic side view showing an example of a modification of the layer structure of the decorative film.

4C is a schematic side view showing an example of a modification of the layer structure of the decorative film.

5A is a schematic cross-sectional view showing an example of a modification of the layer structure of the decorative film.

5B is a schematic cross-sectional view showing an example of a modification of the layer structure of the decorative film.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be performed based on representative embodiments or specific examples, but the present invention is not limited to such embodiments.

In this manual, the numerical range indicated by "~" refers to the range that includes the numerical values described before and after "~" as the lower limit and the upper limit. In addition, when a unit is added to one of the numerical values described before and after "~", it means that the unit is the same in the entire numerical range.

In this specification, "(meth)acryl" refers to either or both of "acryl" and "methacryl", and "(meth)acrylate" refers to "acrylate" Either or both of "and "methacrylate", and "(meth)acrylate" means either or both of "acrylate" and "methacrylate".

In this specification, as long as there is no particular limitation, room temperature means 25°C.

[Decorative film]

The decorative film of the first embodiment of the present invention is a decorative film having a polyester film, a decorative layer, and a hard coat layer. When the decorative film has a length of 50 mm and a width of 50 mm, a thermal history of 150°C for 30 minutes is applied The curl value of the resulting decorative film is 5 mm or less.

In addition, the term "a thermal history with a temperature of 150°C for 30 minutes" means that the decorative film is allowed to stand for 30 minutes in a temperature environment of 150°C to be heated.

The method of measuring the curl value of the decorative film will be described with reference to FIG. 1.

First, the decorative film was cut out with a length of 50 mm and a width of 50 mm to produce a film piece (hereinafter sometimes referred to as a decorative film piece) 10 having a length of 50 mm and a width of 50 mm of the decorative film as a test piece. FIG. 1A is a plan view showing the cut-out decorative film 10. In the plan view of the decorative film 10, the measurement target portion of the curl value is schematically indicated by a mark. The measurement target parts were 4 corners of the cut out decorative film 10 and 4 central parts of each side of the square, totaling 8 places.

The obtained decorative film 10 shown in FIG. 1A was placed in a heating furnace at a temperature of 150° C. for 30 minutes.

Then, after 8 hours of humidity conditioning 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 the flat place 12, and the surface of the flat place 12 is set as the measurement reference surface . The distance between the reference surface and the measurement target location in the decorative film 10 (indicated by arrow H in FIG. 1B), that is, the measurement target location and the reference in the vertical line drawn from the measurement target location of the decorative film 10 to the reference surface The distance between the faces was measured as the curl value. Fig. 1B is a side view showing a state where the decorative film sheet 10 is statically placed on a flat place 12, and in Fig. 1B, the distance indicated by the arrow H is set as a curl value.

When the decorative film sheet 10 is curled into a convex shape with respect to the flat portion 12 as shown in FIG. 1C after heating, the decorative film sheet 10 is turned over and arranged in a concave shape, that is, the state shown in FIG. 1B for measurement.

The curl value of the decorative film sheet 10 to be measured is set to the average value of the curl values measured in the eight measurement target locations of the decorative film sheet described above.

In the decorative film of the present embodiment, the curl of the decorative film that has 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 under the aforementioned conditions exceeds 5 mm, when the decorative film is subjected to press processing, the polyester film and the decorative layer are easily peeled off, which is not good.

The decorative film of the second embodiment of the present invention is a decorative film having a polyester film, a decorative layer, and a hard coat layer. When a thermal history of 150°C for 30 minutes is applied to the polyester film, the surface of the polyester film The thermal shrinkage rate in the one direction and the direction orthogonal to the one direction in the plane is 3.0% or less.

Hereinafter, an example of the embodiment of the present disclosure is referred to as the decorative film of the first embodiment, and an example of another embodiment is referred to as the decorative film of the second embodiment. The constituent elements are explained. In addition, in this specification, when referring to both the first embodiment and the second embodiment, they may be collectively referred to as "the embodiment of the present disclosure".

[Polyester film]

The decorative films of the first embodiment and the second embodiment have a polyester film as a base material.

As one of the methods used to achieve the condition that the decorative film curled to be 5mm or less in the heat history described above, the use of a polyester film with a small heat shrinkage rate can be cited as Substrate.

As a polyester film with a small thermal shrinkage rate, the following polyester film can be cited: When a thermal history of 150°C for 30 minutes is applied to the polyester film as used in the decorative film of the second embodiment described above, The thermal shrinkage rate of the polyester film in one direction in the plane and in the direction orthogonal to the one direction in the plane is 3.0% or less.

In addition, other methods include increasing the thickness of the polyester film as the substrate; stretching the polyester film at a high magnification to increase the elastic modulus of the film for the substrate. These methods are also effective.

As the polyester film used in the decorative film of the first embodiment, when a thermal history of 150°C for 30 minutes is applied to the polyester film, one direction in the surface of the polyester film and the same A polyester film whose heat shrinkage rate in the direction orthogonal to the plane is all 3.0% or less.

In the decorative film of the second embodiment, when a thermal history of 150°C for 30 minutes is applied to the polyester film as a base material, one direction in the plane of the polyester film and a direction orthogonal to the one in the plane of the polyester film The heat shrinkage rate in the direction is a polyester film of 3.0% or less.

<Characteristics of Polyester Film>

(Heat shrinkage)

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 (Machine Direction, hereinafter sometimes referred to as "MD direction") and is aligned with respect to one direction. The direction of intersection (for example, when one direction is set as the "MD direction", the direction orthogonal to the film transport direction (transverse direction, sometimes referred to as "TD direction" hereinafter)) two directions, In the case where the following thermal history is provided, the thermal shrinkage rate is 3.0% or less. The decorative film of the second embodiment has, as a base material, one direction and the same A polyester film having a heat shrinkage rate of 3.0% or less in all directions perpendicular to the plane in one direction.

The thermal history when measuring the heat shrinkage rate of the polyester film is to stand for 30 minutes at a temperature of 150°C.

Hereinafter, a uniaxially stretched polyester film which is a preferred aspect of the base material in the decorative film of the present disclosure will be described as an example.

The thermal shrinkage rate of the polyester film after a thermal history at a temperature of 150°C and 30 minutes in one direction of the film and a direction orthogonal to one direction 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 with a thermal shrinkage rate of 3.0% or less measured under the conditions described above, the thermal stability of the polyester film as the base material is further improved, and wrinkles during the manufacture of decorative films can be more effectively suppressed The occurrence of peeling and chipping during the press processing of the decorative film.

In addition, the absolute value of the difference between the thermal shrinkage rate of the polyester film in one direction in the surface of the polyester film and the thermal shrinkage rate in the direction orthogonal to the one direction in the surface of the polyester film under the aforementioned conditions is preferably 0.6% Below, it is more preferably 0.4% or less, and still more preferably 0.3% or less.

Since the difference in the thermal shrinkage rate of the polyester film in the two directions orthogonal to each other in the plane is small, the physical properties of the polyester film become more uniform. When other layers are laminated on the polyester film to make a decorative film, The wrinkles of the decorative film can be more effectively suppressed when the decorative film is fixed to the member during press processing or when the press processed decorative film is fixed.

In this specification, the heat shrinkage rate under the conditions of a temperature of 150°C for 30 minutes as the thermal history, that is, the heat shrinkage rate of the film after heating at 150°C for 30 minutes is sometimes referred to as "heat shrinkage rate (150 ℃, 30 minutes)”.

The method of measuring thermal shrinkage will be described.

For the sample piece M cut into a polyester film having a width of 30 mm and a length of 120 mm in one direction in the plane, two reference lines were cut in advance at positions that became 100 mm apart in the longitudinal direction. After placing 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. Let the measured interval after the treatment be A [mm]. The value [%] calculated using the formula "100×(100-A)/100" based on the interval 100mm before treatment and the interval A mm after treatment is set as the heat shrinkage rate of the specimen 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 9 locations in total was used as the measurement value.

For example, when one direction is the MD direction, the thermal shrinkage in the MD direction is also referred to as MD thermal shrinkage, and the ratio is referred to as MD thermal shrinkage. Therefore, the heat shrinkage rate in the direction orthogonal to the film width direction when the polyester film is produced becomes the shrinkage rate in the film transport direction, and can be referred to as the MD heat shrinkage rate.

In this specification, the heat shrinkage rate (150°C, 30 minutes) in the direction orthogonal to the one direction described above after being allowed to stand still at 150°C for 30 minutes is defined as follows.

In the case of measuring the thermal shrinkage rate in the direction orthogonal to the one direction already described, cut to a width of 30 mm and a length of 120 in the direction orthogonal to the one direction described. The polyester resin film of mm is used as the sample piece M. For the sample piece M, two reference lines are cut in advance at positions that become 100 mm apart in the length direction. After the sample piece M was allowed to stand in a 150°C heating oven 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. Let the measured interval after the treatment be A [mm]. Set the value [%] calculated using the formula "100×(100-A)/100" based on the interval 100mm before treatment and the interval A mm after treatment as orthogonal to one direction of the specimen M The heat shrinkage rate in the direction (150°C, 30 minutes).

For example, when one direction is the MD direction, the direction orthogonal to the one direction is the TD direction, and the thermal shrinkage can be referred to as TD thermal shrinkage, and the ratio can be referred to as TD thermal shrinkage.

The polyester film having the heat shrinkage rate (150°C, 30 minutes) of 3.0% or less described above is preferably a uniaxially oriented polyester film.

The non-stretched polyester film that has been melt-formed or solution-formed is laterally stretched, heat-fixed, and heat-relaxed by the method described later, thereby easily obtaining a polyester film having the aforementioned preferable heat shrinkage rate.

(thickness)

The thickness of the polyester film is preferably 40 μm to 500 μm, more preferably 60 μm to 400 μm, and still more preferably 80 μm to 300 μm.

When the thickness of the polyester film is within the above-mentioned range, the decorative film has sufficient rigidity and can be suitably used as a substitute for glass, and it is possible to suppress the decrease in punchability and the decrease in operability due to excessive rigidity. In addition, the thickness of the polyester film Within the above range, the dimensional stability of the decorative film becomes better.

The thickness of the polyester film can be measured using a contact-type film thickness meter, for example.

In the measurement, 50 points were sampled in one direction of the polyester film and in a direction orthogonal to the one direction, and the average thickness of the measured values of the thickness at these points was determined to be the thickness of the polyester film.

-Re (Retardation in the film surface)-

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 of 3000 nm to 50000 nm. Hereinafter, as long as there is no particular limitation, the retardation Re in the film surface in this specification means a value at a measurement wavelength of 589 nm.

If the Re of the polyester film is 3000 nm or more, the rainbow-like unevenness is not easy to be recognized, and if it is 50,000 nm or less, the necessary film thickness does not become too thick, excessive rigidity can be suppressed, and handling becomes easy.

From the viewpoint, the Re of the polyester film is more preferably 5000 nm to 40,000 nm, and still more preferably 7000 nm to 33000 nm.

-Re/Rth-

In addition, the polyester film preferably has a ratio (Re/Rth) of the retardation Re in the film plane at a measurement wavelength of 589 nm to the retardation Rth in the film thickness direction at a measurement wavelength of 589 nm (Re/Rth) of 0.6 to 1.2.

If the Re/Rth of the polyester film is 0.6 or more, the rainbow-like unevenness is not easily recognized, and if it is 1.2 or less, the film is less likely to become brittle. Hereinafter, unless otherwise specified, the retardation Rth in the film thickness direction in this specification refers to a value at a measurement wavelength of 589 nm.

From the 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 still more preferably 6000 nm to 40,000 nm.

If the Rth of the polyester film is 3000nm or more, it is easy to produce the film, if it is 80,000nm or less, when the hard coat layer using the polyester film is applied to the display screen of an image display device, for example, rainbow-like appearance is not easy to appear in the screen. Not uniform and better.

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 the formula (1), nx is the refractive index in one direction in the plane of the polyester film, ny is the refractive index in the direction orthogonal to the one direction in the plane of the _{polyester film, and y 1} is the thickness of the polyester film.

The thickness direction retardation Rth of the polyester film of this embodiment is represented by the following formula (2).

Formula (2): Rth={(nx+ny)/2-nz}×y ₁

In the formula (2), nz is the refractive index in the thickness direction of the polyester film.

In addition, the Nz value of the polyester film is represented by the following formula (3).

Formula (3): Nz=(nx-nz)/(nx-ny)

In this specification, Re, Rth, and Nz at the 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 and used as a measurement sample. For the obtained measurement sample, the refractive index (nx, ny) and thickness of the orthogonal biaxial were obtained using an Abbe refractometer (manufactured by Atago, NAR-4T, measurement wavelength 589nm) The refractive index (nz) in the direction, and the absolute value of the biaxial refractive index difference (|nx-ny|) is set as the anisotropy of the refractive index (Δnxy). 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 into nm. The measured nx, ny, nz, respectively, the value calculated from y ₁ to Re, Rth, Nz.

The Re and Rth at the measurement wavelength of 589nm can be determined by the type of polyester resin used in the film, the amount of polyester resin and additives, the addition of retardation developers, the film thickness of the film, the extension direction and elongation rate of the film. Wait to adjust.

The method of controlling the Re and Re/Rth of the polyester film to the respective ranges is not particularly limited. As a method of controlling the Re and Re/Rth of the polyester film, for example, a stretching method can be cited.

(Material, layer composition and surface treatment of polyester film)

The polyester film used in the decorative film of the present disclosure contains 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 polyester resin as a main component, or a multilayer film having at least one layer having 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. Surface treatment can be corona treatment, saponification treatment, heat treatment, using ultraviolet radiation, electron beam Surface modification such as irradiation may also be thin film formation by coating, vapor deposition, or the like of a polymer compound, metal, or the like.

The polyester film may have an easy-adhesive layer on at least one surface.

The thickness of the easily bonding layer contained in the polyester film is preferably 30 nm to 300 nm, more preferably 40 nm to 200 nm, and still more preferably 50 nm to 150 nm.

If the thickness of the easy-to-bond layer is 30 nm or more, the buffering effect of the easy-to-bond layer is easily obtained, and it is possible to suppress the excessive increase of the shear plane vertical stress and the shear plane yield stress. In addition, if the thickness of the easy-to-adhesive layer is 300 nm or less, the cushioning effect of the easy-to-adhesive layer is not too strong, and it is possible to suppress excessive reduction in shear surface vertical stress and shear surface yield stress.

More preferably, the easy-adhesive layer contains particles, and the height of the particles protruding from the surface of the easy-adhesive layer is more than the film thickness of the easy-adhesive layer.

The height of the particles protruding from the surface of the easy-adhesive layer is an average value of 5 points in the easy-adhesive layer of 1 mm square.

If the height of the particles contained in the easy-adhesive layer that the particles protrude from the surface of the easy-adhesive layer is smaller than the film thickness of the easy-adhesive layer (preferably the coating layer), the smoothness is reduced and wrinkles are likely to occur.

The types of particles that can be contained in the easy bonding layer are not particularly limited. Specific examples include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, alumina, and oxides. Particles such as titanium and zirconium oxide are preferably silicon dioxide, aluminum oxide, titanium oxide, and zirconium oxide. In addition, Japanese Patent Publication No. 59-5216, Japanese Patent Publication No. 59-217755, etc. can also be used The heat-resistant organic particles described in. Examples of other heat-resistant organic particles include particles such as thermosetting urea resin, thermosetting phenol resin, thermosetting epoxy resin, and benzoguanamine resin.

With regard to the particle size, it is preferable that the height of the particles protruding from the surface of the easy-adhesive layer is greater than or equal to the film thickness of the easy-adhesive layer. It is preferable to use particles whose primary average particle size is adjusted, but they may be aggregated so that the height of the particles protruding from the surface of the easy-adhesive layer is greater than or equal to the film thickness of the easy-adhesive layer. In the case of aggregated particles, the height of the particles protruding from the surface of the easy-adhesive layer can be confirmed by measuring the secondary average particle size.

(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 (PET) can be used. PBT), Polycyclohexanedimethylene terephthalate (PCT), etc., but in terms of cost and heat resistance, PET and PEN are more preferred, and PET is even more preferred. Furthermore, as far as PEN is concerned, Re/Rth tends to be slightly smaller.

As the polyester resin, polyethylene terephthalate is most preferred. In addition, polyethylene naphthalate can also be preferably used. For example, polyethylene naphthalate described in JP 2008-39803 A can be preferably used.

Polyethylene terephthalate is a polyester having structural units derived from terephthalic acid as a dicarboxylic acid component and structural units derived from ethylene glycol as a diol component, and 80 moles of all repeating units Ear% or more may be ethylene terephthalate, or may contain structural units derived from other copolymerization components. Examples of other copolymerization components include isophthalic acid, p-oxyethoxy benzoic acid, 4,4'-dicarboxydiphenyl, 4,4'-dicarboxybenzophenone, bis(4 -Carboxyphenyl) ethane, adipic acid, sebacic acid, isophthalic acid-5-sodium sulfonate, 1,4-dicarboxycyclohexane and other dicarboxylic acid components, propylene glycol, butylene glycol, neopentyl Glycol components such as glycol, diethylene glycol, cyclohexanediol, ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. These dicarboxylic acid components or diol components can be used in combination of two or more types as needed. In addition, the carboxylic acid component or the diol component may be used in combination with hydroxycarboxylic acids such as p-hydroxybenzoic acid. As other copolymerization components, a small amount of dicarboxylic acid components and/or glycol components containing amide bonds, urethane bonds, ether bonds, carbonate bonds, and the like can also be used.

As a method for producing polyethylene terephthalate, a so-called direct polymerization method in which terephthalic acid, ethylene glycol, and other dicarboxylic acids and/or other glycols are directly reacted can be applied. Any production method such as the so-called transesterification reaction method in which dimethyl terephthalic acid is transesterified with ethylene glycol and, if necessary, dimethyl ester of other dicarboxylic acids and/or other diols.

(1-2) Physical properties of polyester resin

(1-2-1)Intrinsic viscosity

The Intrinsic Viscosity IV (Intrinsic Viscosity) of the 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 still more preferably 0.54 or more, 0.7 or less. In order to keep the IV within the aforementioned range, 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 rate

The acetaldehyde content of the polyester resin is preferably 50 ppm or less. It is more preferably 40 ppm or less, particularly preferably 30 ppm or less. Acetaldehyde is likely to undergo a condensation reaction with each other, and water is produced as a side reactant, and the hydrolysis of the polyester proceeds due to the produced water. The lower limit of the acetaldehyde content is actually about 1 ppm. In order to set the acetaldehyde content within the above range, the following methods can be used: keeping the oxygen concentration low in each step such as melt polymerization and solid phase polymerization during the production of the resin; keeping the oxygen concentration during storage and drying of the resin To be low; to reduce the thermal history of the resin due to the extruder, melt piping, die, etc. during film production; adjust so that it will not be locally subjected to strong shear due to the structure of the screw of the extruder during melting condition.

(1-3) Catalyst

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/or Al-based catalysts, More preferably, it is 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 Al-based catalysts, compared with other catalysts (such as Sb or Ti), Re is easier to show, and PET can be thinned. That is, the use of an Al-based catalyst means that alignment is easier. The reason is assumed to be as follows.

Al-based catalysts are more reactive than Sb-based catalysts or Ti-based catalysts (polymerization activity) Low, slow reaction, difficult to produce by-products (Diethylene glycol unit: DEG (Diethylene glycol)).

As a result, the regularity of PET is improved, alignment is easy, and Re is easy to appear.

(1-3-1)Al series catalyst

As the Al-based catalyst, the Al-based catalysts described in [0013] to [0148] of WO2011/040161 ([0021] to [0123] of US2012/0183761) can be used. The recorded content can be incorporated into the specification of this application.

The method of manufacturing polyester resin by polymerization using Al-based catalyst is not particularly limited. Specifically, it can be based on [0091] ~ [0094] of WO2012/008488 ([0144] of US2013/0112271) ~[0153]) to aggregate, and the contents described in these bulletins can be incorporated into the specification of this application.

In addition, the Al-based catalyst can be based on, for example, [0052] ~ [0054], [0099] ~ [0104] (WO2012/029725 [0045] ~ [0047], [ 0091] ~ [0096]) were prepared, and the contents described in these bulletins can be incorporated into the specification of this application.

As the amount of Al element relative to the mass of the polyester resin, the amount of Al catalyst is preferably 3 ppm to 80 ppm, more preferably 5 ppm to 60 ppm, and still more preferably 5 ppm to 40 ppm.

(1-3-2)Sb series catalyst

As the Sb-based catalyst, the Sb-based catalysts described in [0050] and [0052] to [0054] of JP 2012-41519 A can be used.

The method of polymerizing the polyester resin using the 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) Additives

It is also preferable to add a known additive to the polyester film. Examples of well-known additives include: ultraviolet absorbers, particles, slip agents, anti-blocking agents, heat stabilizers, antioxidants, antistatic agents, light resistance agents, impact resistance modifiers, lubricants, dyes, and pigments. Wait. However, polyester films generally require transparency, and therefore, it is preferable to limit the addition amount of additives to a minimum.

(1-4-1) Ultraviolet (UV) absorber

In order to prevent deterioration of the liquid crystal of the liquid crystal display due to ultraviolet rays, an ultraviolet absorber may be contained in the polyester film. The ultraviolet absorber is a compound having ultraviolet absorbing ability, and it is not particularly limited as long as it can withstand the heat added in the production step of the polyester film.

As the ultraviolet absorber, there are organic ultraviolet absorbers and inorganic ultraviolet absorbers, and from the viewpoint of transparency, organic ultraviolet absorbers are preferred. The ultraviolet absorber described in [0057] of WO2012/157662 or the cyclic imino ester-based ultraviolet absorber described later can be used.

The cyclic imino ester-based ultraviolet absorber is not limited to the following, and examples include 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1 -Benzoxazine-4-one, 2-phenyl-3,1-benzoxazine-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-benzo Oxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2-parabenzylphenyl-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-Benzoxazin-4-one, 2-p (or meta) phthalimide phenyl-3,1-benzoxazin-4-one, N-phenyl-4- (3,1-benzoxazine-4-one-2-yl)phthalimide, N-benzoxazine-4-(3,1-benzoxazine-4-one-2 -Yl)aniline, N-benzyl-N-methyl-4-(3,1-benzoxazine-4-one-2-yl)aniline, 2-(p-(N-methylcarbonyl) Phenyl)-3,1-benzoxazin-4-one, 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-ethylenebis(3, 1-benzoxazine-4-one), 2,2'-tetramethylene bis(3,1-benzoxazine-4-one), 2,2'-decamethylene bis(3, 1-benzoxazine-4-one), 2,2'-(1,4-phenylene) bis(4H-3,1-benzoxazine-4-one) [Furthermore, also known as 2,2'-p-phenylene bis(3,1-benzoxazin-4-one)], 2,2'-p-phenylene bis(3,1-benzoxazin-4-one) , 2,2'-(4,4'-diphenylene) bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthylene or 1,5 -Naphthyl)bis(3,1-benzoxazine-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-one) 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-benzoxazine-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)-oxazine- 4,6-dione, 6,6'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-bis(2-ethyl-4H,3 ,1-Benzoxazine-4- Ketone), 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'-ethylene Bis(2-methyl-4H,3,1-benzoxazine-4-one), 6,6'-ethylenebis(2-phenyl-4H,3,1-benzoxazine- 4-ketone), 6,6'-butylene bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-butylene bis(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'-sulfonyl bis(2-methyl-4H,3,1-benzo Oxazin-4-one), 6,6'-sulfonyl bis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-carbonyl bis(2-methyl -4H,3,1-benzoxazin-4-one), 6,6'-carbonyl bis(2-phenyl-4H,3,1-benzoxazin-4-one), 7,7 '-Methylene bis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-methylene bis(2-phenyl-4H,3,1-benzene Oxazin-4-one), 7,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-ethylenebis(2-methyl Group-4H,3,1-benzoxazin-4-one), 7,7'-oxybis(2-methyl-4H,3,1-benzoxazin-4-one), 7, 7'-sulfonyl bis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-carbonyl bis(2-methyl-4H,3,1-benzo Oxazin-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-benzoxazin-4-one), 6,7'- Methylene bis(2-phenyl-4H,3,1-benzoxazin-4-one) and the like.

Among the compounds, when the hue is considered, benzoxazinone-based compounds that are hard to have a yellow color can be suitably used. For example, a compound represented by the following formula (4) can be more suitably used.

Formula (4) [化1]

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

Functional group: alkyl, aryl, heteroaryl, halogen, alkoxy, aryloxy, hydroxyl, carboxy, 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 amount of the ultraviolet absorber that can be contained in the polyester film is generally 10.0% by mass or less with respect to the entire film, and preferably in the range of 0.3% by mass to 3.0% by mass. When the ultraviolet absorber is contained in an amount exceeding 10.0% by mass, there is a possibility that the ultraviolet absorber oozes out to the surface and the adhesiveness is reduced, which may cause a decrease in the functionality of the surface.

In addition, when the polyester film has a laminated structure, it is preferably at least a three-layer structure, and the ultraviolet absorber is preferably blended in the intermediate layer (layer other than the outermost layer). By blending the ultraviolet absorber into the intermediate layer, the ultraviolet absorber can be prevented from oozing out to the surface of the film, and as a result, the adhesiveness and other characteristics 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 the polyester film, other additives may also be used. For example, the additives described in [0058] of WO2012/157662 can be used, and the contents described in the publication can be incorporated into the specification of this application.

(Production of polyester film)

The polyester film is preferably produced by the following production method.

The manufacturing method includes a horizontal stretching step, using a tenter type stretching device equipped with a plurality of clamps that move along a pair of rails respectively provided on both sides of a film conveying road, and clamp the unstretched polyester with the clamps. In the state of the film, stretch in a direction orthogonal to the film conveying path; heat fixation step, heat fixation by heating the polyester film stretched in the transverse direction; and heat relaxation step, heat fixation step The latter polyester film is heated, and the film transport direction of the polyester film and the length of the direction orthogonal to the film transport direction are reduced, and in the heat relaxation step, the polyester film after the heat fixing step is relative to The ratio of the reduction in the length in the 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 polyester film that has been heat-fixed The relaxation rate in the conveying direction is set to 0.1% to 7%, whereby the film conveying direction and the direction perpendicular to the film conveying direction can be manufactured with heat shrinkage when the temperature is 150°C for 30 minutes. A polyester film with a rate of 3.0% or less, which is suitable as a base material for a decorative film.

Here, the so-called "unstretched polyester film" means the refractive index of MD and TD are both A polyester film of 1.590 or less, for example, a polyester film having a refractive index of 1.590 or less in MD and TD, even though it is slightly stretched in MD, etc., is also included in an unstretched polyester film.

Hereinafter, as a preferred aspect of the polyester film manufacturing method, a case where a uniaxially oriented polyester film is manufactured by forming an unstretched polyester film by melt extrusion and then stretching in the lateral direction will be described.

<melt kneading>

The unstretched polyester film is preferably formed into a film shape by melt-extruding a polyester resin.

Preferably, the polyester resin or the masterbatch of the polyester resin and additives produced by the masterbatch method is dried to a moisture content of 200 ppm or less, and then introduced into a uniaxial or biaxial extruder and used It melts. In order to suppress the decomposition of the polyester resin in the extruder, melting in nitrogen or vacuum is also preferable. For detailed conditions, for example, [0051]~[0052] of Japanese Patent No. 4962661 ([0085]~[0086] of US2013/0100378) can be cited, and implementations based on these publications are described in these publications. The content can be incorporated into the description 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. In addition, it is also preferable to use a filter with a pore size of 3 μm to 20 μm to remove foreign matter.

<Extrusion or Coextrusion>

Preferably, the melt containing the melt-kneaded polyester resin is extruded from a die, and it can be extruded in a single layer or in multiple layers (coextrusion). When extruding in multiple layers, for example, a layer containing an ultraviolet absorber (UV agent) can be combined with a layer containing no ultraviolet From the viewpoint of suppressing the bleeding of the UV agent to suppress the deterioration of the polarizing element caused by the UV agent, the laminated layer of the absorbent is preferably a three-layer structure in which the UV agent is located in the inner layer.

When the UV agent oozes out, the UV agent on the film surface is sometimes transferred to the roller in contact with the film during the film manufacturing step, which increases the friction coefficient between the film and the roller and is prone to scratches, which is unsatisfactory.

When the polyester film is produced by extrusion in multiple layers, the thickness (ratio relative to all layers) of the preferred inner layer (layers other than the outermost layer) of the obtained polyester film is preferably 50% or more, 95% % Or less, more preferably 60% or more and 90% or less, and still more preferably 70% or more and 85% or less. Such layering can be implemented by using a feed block mold or a multi-manifold mold.

<Casting>

As a method of manufacturing the polyester film, the following method is preferred: for example, according to the description of [0059] in Japanese Patent Laid-Open No. 2009-269301, the melt extruded from the die is extruded onto the casting drum and carried out. It is cooled and solidified to obtain an unstretched polyester film (original film).

In the production method of the polyester film, the refractive index of the unstretched polyester film in the film transport direction (MD direction) is preferably 1.590 or less, more preferably 1.585 or less, and still more preferably 1.580 or less.

When the polyester film is manufactured, the crystallinity of the unstretched polyester film is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less. In addition, the crystallinity of the unstretched polyester film mentioned here refers to the central part of the film width direction (TD direction) Crystallinity.

When adjusting the crystallinity, the temperature of the end of the casting drum can be lowered, or the air can be blown toward the casting drum.

Regarding the crystallinity, it can be calculated from the density of the film. That is, the density X (g/cm ³ ) of the film, the density Y=1.335g/cm ³ when the crystallinity is 0%, and the density Z=1.501g/cm ³ when the crystallinity is 100% can be used, and according to the following The calculation formula is used to derive the degree of crystallinity (%).

Crystallinity={Z×(X-Y)}/{X×(Z-Y)}×100

In addition, the density is measured in accordance with Japanese Industrial Standards (JIS) K7112.

<Formation of optional polymer layer>

On the non-stretched polyester film that has been melt-extruded, any polymer layer corresponding to the purpose can be formed by coating before or after the stretching described later.

As an arbitrary polymer layer, the functional layer which a polarizing plate can have normally can be mentioned, Especially, it is preferable to form an easy-adhesion layer. The easy bonding layer can be applied, for example, by the method described in [0062] to [0070] of WO2012/157662.

<Preheating>

Fig. 2 schematically shows an example of the configuration of the tenter stretching device used in the lateral stretching step.

As the preheating step 100 before the start of stretching in the lateral stretching step 200, it is preferable to preheat the unstretched polyester film at a temperature increase rate of 600°C/min or less. hot. If the temperature increase rate of the film before the start of the stretching in the lateral stretching step 200 is 600°C/min or less, it will be stretched in a state where the molecular chains are fully activated, and the shear plane vertical stress and shear plane drop can be suppressed The stress increases excessively.

From the viewpoint, the temperature increase rate in the preheating step 100 is more preferably 500° C./min or less, and still more preferably 400° C./min or less.

<Horizontal extension>

In the lateral stretching step 200, as shown in FIG. 2, a tenter type stretching device (also referred to as a "tenter frame") having a plurality of clamps 13 that move along a pair of rails provided on both sides of the film conveying road is used. "), in a state where the two edges of the non-stretched polyester film are clamped by the clamps 13 for lateral extension. Furthermore, it is also possible to clamp the unstretched polyester film with a clamp from the stage of the preheating step 100.

The tenter stretching device having the clamps 13 that move along a pair of rails installed on both sides of the film conveying road is not particularly limited. A pair of rails usually uses a pair of circular rails. Furthermore, the meaning of the clamp is the same as that of the clamping member.

The unstretched polyester film is stretched laterally. While conveying the unstretched polyester film along the film conveying path, the unstretched polyester film is stretched laterally in the direction (TD) orthogonal to the film conveying direction (MD). That is, the lateral extension can be achieved by clamping both ends of the film with clamps, heating on one side, and 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 satisfying the preferable ranges of Re and Re/Rth, it is preferable to perform at least lateral stretching.

The surface temperature at the beginning of the stretching in the lateral stretching step is preferably 80°C Above and below 95°C, more preferably above 82°C and below 93°C, and still more preferably above 84°C and below 92°C.

If the surface temperature at the start of the stretching in the lateral stretching step is 80° C. or higher, the alignment and alignment crystallization will not proceed excessively in the stretching stage, and the shear plane vertical stress and the shear plane yield stress can be prevented from increasing excessively. In addition, the increase in Rth is suppressed, and the Re/Rth ratio becomes 0.6 or more, so that the visibility of rainbow-like unevenness can be suppressed.

If the surface temperature at the start of the stretching in the lateral stretching step is 95°C or lower, the growth of spherulites caused by insufficient alignment is suppressed, and the shear plane vertical stress and the shear plane yield stress are prevented from being excessively reduced, and film formation can be suppressed. It is cloudy, and Re is easy to rise sufficiently.

In the production method of the polyester film, the surface temperature at the end of the 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 or lower. Below ℃.

If the surface temperature at the end of the stretching in the lateral stretching step is 90° C. or more, the alignment and alignment crystallization will not proceed excessively in the stretching stage, and the shear plane vertical stress and the shear plane yield stress can be prevented from increasing excessively. In addition, the increase in Rth is suppressed, and the Re/Rth ratio becomes 0.6 or more, so that the visibility of rainbow-like unevenness can be suppressed.

If the surface temperature at the end of the extension step in the lateral extension step is 105°C or less, the growth of spherulites caused by insufficient alignment is suppressed, and excessive reduction in shear plane vertical stress and shear plane yield stress and film formation can be suppressed. It is cloudy, and Re, which affects the suppression of rainbow-like unevenness, tends to rise sufficiently.

From the beginning of the extension in the lateral extension step to the end of the extension, the surface temperature Slowly rise. Here, the so-called "slowly rising" may mean a continuous rise or a stepwise rise.

The difference between the surface temperature at the end of the extension and the beginning of the extension is preferably 1°C or more, more preferably 3°C or more, and most preferably 5°C or more.

If the surface temperature rises slowly from the beginning of the extension to the end of the extension, it is more difficult to form spherulites, and excessive alignment can be suppressed, it is easy to have both Re and Re/Rth in their respective preferred ranges, and rainbow-like unevenness is not easy to be affected. Visual recognition.

The lateral stretching magnification in the lateral stretching step is preferably controlled to 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 still more preferably 3.7 times or more and 4.3 times or less.

If the lateral stretch magnification is 3.3 times or more, it is possible to suppress the excessive reduction of the shear surface vertical stress and shear surface yield stress of the film, and also suppress the reduction of Re, which is effective in suppressing rainbow-like unevenness. If the lateral stretch magnification is 4.8 times or less, it is possible to suppress the excessive increase in the shear surface vertical stress and shear surface yield stress of the film and become brittle.

In the lateral stretching step, the surface temperature of the film when the lateral stretching ratio is in the 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 84°C Above ℃, below 91℃.

If the surface temperature of the film when the lateral stretching magnification in the lateral stretching step is in the range of 1 to 2 times is 80°C or higher, alignment and alignment crystallization will not proceed excessively during the stretching stage, and the shear plane vertical stress can be suppressed And the shear surface yield stress is excessively increased. In addition, the increase in Rth is suppressed, and the Re/Rth ratio becomes 0.6 or more, so that the visibility of rainbow-like unevenness can be suppressed.

If the surface temperature of the film when the lateral stretch magnification in the lateral stretch step is in the range of 1 to 2 times is 92°C or lower, the growth of spherulites due to insufficient alignment is suppressed, and the shear plane vertical stress and The shear surface yield stress decreased excessively, 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 magnification 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 still more preferably 87 Above ℃, below 96℃.

In the lateral stretching step, if the surface temperature of the film when the lateral stretching magnification is in the range of 2 to 3 times is 85°C or higher, alignment and alignment crystallization do not proceed excessively during the stretching stage, and vertical shear planes can be suppressed The stress and shear surface yield stress increase excessively. In addition, the increase in Rth is suppressed, and the Re/Rth ratio becomes 0.6 or more, so that the visibility of rainbow-like unevenness can be suppressed.

In the lateral stretching step, if the surface temperature of the film when the lateral stretching magnification is in the range of 2 to 3 times is 97°C or lower, the growth of spherulites due to insufficient alignment is suppressed, and the shear plane vertical stress can be suppressed And the shear surface yield stress is excessively reduced. In addition, Re, which is effective in suppressing rainbow-like unevenness, is sufficiently increased, so that the visible rainbow-like unevenness can be suppressed.

In the lateral stretching step, the surface temperature of the film when the lateral stretching ratio is 3 times or more is preferably 90°C or higher and 102°C or lower, more preferably 92°C or higher and 101°C or lower, and still more preferably 93°C or higher , Below 100℃.

In the lateral stretching step, if the surface temperature of the film when the lateral stretching magnification is in the range of 3 times or more is 90°C or higher, the alignment and alignment crystallization in the stretching stage are not It will proceed excessively, which can suppress the excessive increase of the shear surface vertical stress and shear surface yield stress. In addition, the increase in Rth is suppressed, and the Re/Rth ratio becomes 0.6 or more, so that the visibility of rainbow-like unevenness can be suppressed.

In the lateral stretching step, if the surface temperature of the film when the lateral stretching magnification is 3 times or more is 102°C or lower, the growth of spherulites due to insufficient alignment is suppressed, and the shear plane vertical stress and shear can be suppressed. The tangential yield stress is excessively reduced. In addition, Re is sufficiently increased, and rainbow-like unevenness can be suppressed.

Furthermore, since the surface temperature gradually rises from the beginning of the stretching to the end of the stretching, in the lateral stretching step, the surface temperature and the lateral stretching magnification of the film when the lateral stretching magnification is in the range of 1 to 2 times The surface temperature of the film in the range of 2 to 3 times and the surface temperature of the film in the range of 3 times or more of the lateral stretch magnification will not be lower than the surface temperature of the range during stretching with a small lateral stretch magnification, respectively. That is, the surface temperature of the film when the lateral stretch magnification is in the range of 2 to 3 times does not fall below the surface temperature of the film when the lateral stretch magnification is in the range of 1 to 2 times, and the lateral stretch magnification is 3 times or more. The surface temperature of the film at this time does not become less than the surface temperature of the film when the lateral stretch magnification is in the range of 2 to 3 times.

In the lateral stretching step, it is preferable to set the temperature increase rate of the surface temperature during stretching to 60°C/min or less, more preferably 50°C/min or less, and still 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, the rapid movement of molecular chains during the stretching process can be suppressed, thereby suppressing the shear plane vertical stress and excessive reduction of the shear plane yield stress. small. In addition, the rainbow shape is not Uniformly suppresses the effective increase of Re and makes it difficult to see rainbow-like unevenness.

<Heat Fix>

This embodiment includes a heat-fixing step 300 which performs heat-fixing by heating the polyester film after the transverse stretching to the highest temperature in the transverse stretching device. Here, the highest temperature in the heat fixation refers to the highest point of the film surface temperature reached by the film in the heat fixation area. It can be obtained by using a radiation thermometer to measure the temperature of the film surface in the heat-fixing area.

After stretching, a heat treatment called "heat fixation" is performed in order to promote crystallization. It is possible to promote crystallization and increase the strength of the film by performing a heat fixing step of heating at a temperature exceeding the stretching temperature.

In the heat setting, the polyester film undergoes volume shrinkage for crystallization.

As a method of heat fixation, several slits that send hot air toward the extension part are provided in parallel in the width direction. It is achieved by making the temperature of the gas blown from the slit higher than the extension part.

In addition, a heat source (infrared (Infrared, IR) heater, halogen heater, etc.) may be installed near the outlet of the extension (portion) to increase the temperature.

The maximum surface temperature of the polyester film in the heat fixing 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 maximum surface temperature in the heat fixation step is 130°C or higher, it can suppress the shear surface vertical stress and shear surface yield stress from excessively decreasing, if it is 230°C or less, the shear surface vertical stress and shear can be suppressed The surface yield stress is excessively increased.

From the end of the extension step to the highest temperature in the heat fixation step The temperature increase rate of the film 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 increase rate of the film in the heat fixing step from the end of the stretching step is 1000°C/min or less, the rapid relaxation of the molecules before crystallization can be suppressed, and the shear plane vertical stress and the shear plane yield stress can be prevented from being excessively reduced. It is small, or Re does not rise sufficiently, and rainbow-like unevenness is recognized.

The time for the surface temperature to exceed 130°C is preferably 180 seconds or less, more preferably 120 seconds or less, and still more preferably 60 seconds or less.

If the surface temperature exceeds 130°C for 180 seconds or less, crystallization does not proceed excessively, and it is possible to suppress excessive increase in shear surface vertical stress and shear surface yield stress, or excessive increase in Rth, and rainbow-like unevenness can be seen Case.

<Heat Relief>

This embodiment preferably includes a heat relaxation step 400. The heat relaxation step 400 heats the polyester film after the heat fixation step 300, and reduces at least the film transport direction (MD) of the polyester film and the direction of the film transport. The length of the intersection direction (TD).

Furthermore, the heat relaxation step is not strictly limited to the aspect performed after the heat fixation step, and the heat fixation step and the heat relaxation step may be carried out at the same time. When the heat fixing step and the heat relaxation step are performed at the same time, the time before heating to the highest temperature in the lateral stretching device can be used as the heat fixing step, and it can be continued at a temperature that does not exceed the maximum temperature in the lateral stretching device Heat relaxation.

It is preferable to perform heat treatment and relaxation (shrink the film) at the same time after the heat fixing step, and preferably in the TD direction (the direction orthogonal to the film conveying direction: also referred to as the transverse direction), MD (film conveying direction: also called longitudinal direction) is relaxed in both directions.

Preferably, reducing the length of the polyester film in the direction orthogonal to the film conveying direction in the heat relaxation step includes reducing the distance between a pair of rails provided on both sides of the film conveying path, and reducing the polyester in the heat relaxation step The length of the film conveyance direction of the film includes the interval between the plurality of jigs that are moved and reduced.

In the MD direction, before releasing the polyester film after transverse stretching from the clamp, it is preferable to include a shrinking step in addition to the heat fixing step of heating the polyester film after transverse stretching to the highest temperature in the transverse stretching device. The interval between a plurality of jigs that move along a pair of rails provided on both sides of the film conveying path.

Relaxation by narrowing the gap between the clamps can be achieved, for example, by using a pantograph-shaped chuck in a tenter and narrowing the gap between the pantographs. In addition, it can also be achieved by using an electromagnet. This is achieved by driving the fixture and reducing the driving speed.

The reduction in the length of the polyester film in the film conveying direction in the heat relaxation step can be performed by applying tension in the film conveying direction of the polyester film to reduce the length while conveying under heating conditions.

Under heating conditions, while conveying the polyester film, apply tension below the residual stress of the film to the polyester 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 of the film conveying direction can be reduced. In addition, the residual stress of the polyester film can be determined by, for example, measuring the shrinkage force of the film during heating using a thermomechanical analyzer (TMA-60, manufactured by Shimadzu Corporation).

From the viewpoint of further improving the scratch resistance of the polyester film and suppressing the heat shrinkage rate, it is preferable to set the ratio of the reduction of the TD length of the heat-fixed polyester film, that is, the TD relaxation rate to 0.1%~ 7.0%, more preferably 0.5%~5.0%, still more preferably 1.0%~4.0%. With the relaxation rate of TD being 0.1% or more, the heat shrinkage rate can be reduced. With the relaxation rate of TD being 7% or less, it is difficult to produce slack, wrinkles, damage and other surface faults in the TD during the relaxation treatment. It is suppressed, which is better.

In the heat relaxation step, it is preferable to set the reduction ratio of the MD length of the heat-fixed polyester film, that is, the relaxation rate of MD to 0.1% to 7%, more preferably 0.5% to 5.0%, and still more Preferably, it is 1.0%~4.0%. If the relaxation rate of MD is 0.1% or more, the thermal shrinkage rate of MD can be reduced, making it difficult to cause peeling of the decorative layer or deformation of the film during press processing of a decorative film obtained using a polyester film. If the relaxation rate of MD is 7% or less, it is difficult to generate slack in MD during the relaxation treatment, and the occurrence of surface faults such as wrinkles and scratches is suppressed, which is preferable.

As a preferable condition in the heat relaxation step for suppressing the heat shrinkage rate of the polyester film to 3.0% or less, the following conditions can be cited: the conveying tension of the polyester film in the heat relaxation step is 10N/m width ~ 80N /m width range, the film surface temperature during heating of the polyester film is 110°C to 190°C, and the heat treatment time is 10 seconds to 600 seconds. When the film surface temperature is in the range of 70℃±20℃, the cooling rate is 100℃/min~2000℃/min.

The conveying tension of the polyester film in the heat relaxation step is preferably in the range of 10 N/m width to 80 N/m width, more preferably 15 N/m width to 60 N/m width, and even more preferably 20 N/m width. 40N/m width range. By conveying tension as 10N/m width or more, the film damage caused by friction with the roller in the heat relaxation step is suppressed, and the conveying tension is 80N/m width or less, the heat shrinkage rate of the polyester film can be reduced. The peeling of the decorative layer when the decorative film obtained by using the polyester film is subjected to press processing, and the deformation of the decorative film are suppressed.

Regarding the relaxation temperature, as long as it can be heat-fixed to heat the stretched polyester film to the highest temperature in the stretching device, it may be the same temperature as the heat-fixing (that is, it can reach the highest temperature in the lateral stretching device), It can also be lower than the heat fixation temperature. Here, the highest temperature in the thermal relaxation refers to the highest point of the film surface temperature reached by the film in the thermal relaxation zone. It can be obtained by measuring the temperature of the film surface in the heat relaxation zone with a radiation thermometer.

Among them, 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 heat shrinkage rate of the polyester film can be reduced, and peeling of the decorative layer and deformation of the decorative film when the decorative film obtained by using the polyester film is pressed can be suppressed. When the film surface temperature is 190°C or lower, the occurrence of failures such as film wrinkles 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 rate of the polyester film can be reduced, and the peeling of the decorative layer and the deformation of the decorative film when the decorative film obtained by using the polyester film is pressed can be suppressed. When the heat treatment time is 600 seconds or less, the occurrence of surface faults such as wrinkles of the film in the heat relaxation step is suppressed.

<cooling>

This embodiment preferably includes a step of cooling the polyester film before releasing the heat-fixed polyester film from the clamp or before the heat-relaxed polyester film. From the viewpoint of ease of lowering the temperature of the jig when releasing the polyester film from the jig, it is preferable that the polyester film after heat fixing or heat relaxation is cooled before being released from the jig.

The cooling temperature of the polyester film after heat setting or heat relaxation is preferably 80°C or lower, more preferably 70°C or lower, and particularly preferably 60°C or lower.

As a method of cooling the polyester film after heat setting, specifically, the method of blowing cold wind on a polyester film is mentioned.

When cooling is performed after the heat 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~2000°C/min, more preferably 300°C/min~1500 ℃/min, more preferably 500℃/min~1000℃/min.

When the cooling rate is 100° C./min or higher, the conveying distance in the cooling zone becomes appropriate, which is also better in terms of device size and cost. In addition, when the cooling rate is 2000° C./min or less, the occurrence of surface faults such as wrinkles during cooling of the polyester film is suppressed.

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

By performing the described preheating step, lateral stretching step, heat fixing step and heat relaxation step, the better heat shrinkage rate, Re, Rth and Re/Rth make it easy to produce a polyester film that can exhibit effects such as reducing the rainbow-like unevenness of the polyester film and suppressing curling of a decorative film made using the polyester film.

<Release the film from the clamp>

After the steps, release the polyester film from the clamp.

It is preferable to control the surface temperature of the polyester film when the polyester film is released from the jig in the 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 still more preferably 60°C or higher and 100°C or lower.

In the production method of the polyester film, the thickness of the polyester film after film formation (after the release step in the clamp) is preferably 40 μm or more and 500 μm or less, more preferably 60 μm or more and 400 μm or less, and even more preferably It is 80 μm or more and 300 μm or less. By setting the thickness of the polyester film in the above range, a decorative film having a polyester film as a base material has sufficient rigidity, and can suppress the reduction in punchability and handleability due to excessive rigidity, and dimensional stability Become better.

<Recycling, cutting and winding of film>

After being released from the clamp, the film is trimmed, cut, knurled, and reeled for recycling as needed.

In the manufacturing method of the polyester film, from the viewpoint of efficiently ensuring the width of the film product and preventing the size of the device from becoming too large, the width of the film after being released from the jig is preferably 0.8m-6m, and more preferably 1m~5m, particularly preferably 1m~4m. The optical film requiring precision is usually formed in a thickness of less than 3 m, but in this embodiment, it is preferable to form the film in a width as described above.

In addition, the film formed with a wide thickness can be cut into preferably 2 or more and 6 or less, more preferably 2 or more and 5 or less, and still more preferably 3 or more and 4 or less After that, take it up.

It is preferable to perform knurling processing (knurling) on both ends after cutting.

The winding is preferably to wind a winding core having a diameter of 70 mm or more and 600 mm or less by 1,000 m or more and 10,000 m or less. Per unit cross-sectional area of the film winding tension is preferably ^{30N / cm 2 ~ 300N / cm} 2, more preferably ^{50N / cm 2 ~ 250N / cm} 2, and further more preferably ^{70N / cm 2 ~ 200N / cm} 2. In addition, it is also better to attach a masking film before winding.

[Hard Coating]

The decorative film of the present disclosure has a hard coat layer on at least one surface 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 disposing the hard coat layer on the outermost surface, scratch resistance becomes good. From the viewpoint of further improving the scratch resistance, the pencil hardness on the surface of the hard coat layer is preferably H or more, more preferably 3H or more, and even more preferably 5H or more.

<Hard Coating>

Hereinafter, the hard coat layer in the decorative film of the present disclosure will be described.

The hard coat layer can be formed by either a wet coating method or a dry coating method (vacuum film formation), and is preferably formed by a wet coating method excellent in 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, Japanese Patent Special opening 2011-131409, JP 2011-131404, JP 2011-126162, JP 2011-75705, JP 2009-286981, JP 2009-286981 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 Laid-Open Hard coats described in 2002-156505, JP 2001-272503, WO12/018087, WO12/098967, WO12/086659, and WO11/105594.

(Thickness of hard coat)

The thickness of the hard coat layer in the decorative film of the present disclosure is preferably 5 μm or more. If the thickness of the hard coat layer is 5 μm or more, a hard coat layer with 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 still more preferably 15 μm or more.

Furthermore, from the viewpoint of easy press processing, the thickness of the hard coat layer is preferably 40 μm or less, and more preferably 35 μm or less.

(Material of the hard coat layer)

The hard coat layer contains at least the structure derived from the following a), the structure derived from the following b), the following c) and the following d), when the total solid content of the hard coat is 100% by mass The hard coat layer preferably contains: 15% to 70% by mass of the structure derived from the following a), 25% to 80% by mass of the structure derived from the following b), The following c) of 0.1% by mass to 10% by mass, and the following d) of 0.1% by mass to 10% by mass.

a) A compound with an alicyclic epoxy group and a group containing an ethylenically unsaturated double bond in the molecule, and the molecular weight is less than 300

b) Compounds having three or more groups containing ethylenically unsaturated double bonds in the molecule

c) Free radical polymerization initiator

d) Cationic polymerization initiator

By providing the hard coat layer of such a structure, the pencil hardness of the decorative film is high, the smoothness is excellent, and the change in the appearance of the film after heat and humidity is suppressed over time.

(The composition of the hard coat layer)

The hard coat layer is preferably formed by a coating method on at least one surface of the polyester film of the aforementioned embodiment.

The hard coat layer is more preferably formed by hardening the hard coat layer forming composition containing a), b), c), and d), and the total solid content of the hard coat layer forming composition is 100% by mass In the case of, the composition for forming a hard coat layer contains 15% to 70% by mass of a), 25% to 80% by mass of b), 0.1% to 10% by mass of c), 0.1% to 10% by mass D) of mass%.

<Hard coat layer and hard coat layer forming composition>

The details of each component contained in the hard coat layer and the hard coat layer forming composition are described below.

-a) It has an alicyclic epoxy group and an ethylenic group in the molecule Compounds with unsaturated double bonds and a molecular weight of 300 or less-

When the total solid content of the hard coat layer is 100% by mass, the hard coat layer contains 15% by mass to 70% by mass of the 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 a compound 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 containing at least a), b), c), and d), and the total solid content of the hard coat layer forming composition is In the case of 100% by mass, the composition for forming a hard coat layer contains 15% to 70% by mass of a).

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

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

The number of epoxy groups and ethylenically unsaturated double bonds-containing groups in the molecule is one. The reason is that when the number of each functional group is 1 compared with the case of 2 or more, by reducing the number of functional groups (epoxy group and ethylenically unsaturated double The number of bond bases) reduces the molecular weight, and the pencil hardness further increases.

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 a) component to 300 or less, parts other than the epoxy group and the ethylenically unsaturated double bond-containing group are reduced, and the pencil hardness can be improved.

In addition, from the viewpoint of suppressing volatilization during the formation of the hard coat layer, the molecular weight of the a) component is preferably 100 or more, and more preferably 150 or more.

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

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, it is preferably an alicyclic hydrocarbon, and among them, an alicyclic group having 4 to 10 carbon atoms is more preferred, and even more preferably an alicyclic group having 5 carbon atoms is more preferred. 7 alicyclic groups, particularly preferably an alicyclic group having 6 carbons. Specifically, it is preferably Cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, particularly preferably cyclohexyl.

In the case where R in the formula (5) is a cross-linked hydrocarbon, it is preferably a 2-ring system cross-linking (bicyclo ring) and a 3-ring system cross-linking (tricyclo ring), including Cross-linked hydrocarbons with 5 to 20 carbon atoms, including norbornyl, bornyl, isobornyl, tricyclodecyl, dicyclopentenyl, dicyclopentyl, tricyclopentenyl and Tricyclopentanyl, adamantyl, adamantyl substituted by lower alkyl, etc.

When L represents a divalent linking group, it is preferably a divalent aliphatic hydrocarbon group. As the divalent aliphatic hydrocarbon group, the carbon number is preferably 1 to 6, more preferably 1 to 3, and still 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)acrylic groups, vinyl groups, styryl groups, and allyl groups. Among them, (meth)acrylic groups and -C(O)OCH=CH are preferred. _2. Especially preferred is (meth)acryloyl.

As a specific compound of component a), if it has one alicyclic epoxy group and one ethylenically unsaturated double bond-containing group in the molecule, and has a molecular weight of 300 or less, it is not particularly limited and can be used The compound described in paragraph [0015] of Japanese Patent Laid-Open No. 10-17614, the 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 preferred, and a compound represented by the following formula (1A) having a low molecular weight is still more preferred. Furthermore, it is also preferably an isomer of the compound represented by the following formula (1A). In the following formula (1A), L ₂ represents a divalent aliphatic hydrocarbon group having 1 to 6 carbons, more preferably 1 to 3 carbons, and even more preferably a carbon number from the viewpoint of improving smoothness 1 (that is, component a) is epoxycyclohexyl methyl (meth)acrylate).

By using these compounds, it is possible to have both high pencil hardness and excellent smoothness at a higher level.

In the 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.

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 still 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, 15% by mass to 70% by mass of the structure derived from a) is contained. That is, when the total solid content of the composition for hard-coat layer formation is 100 mass %, 15 mass%-70 mass% of a) component is contained. When the content of the structure derived from a) or the a) component is 15% by mass or more with respect to the hard coat layer or the hard coat layer forming composition, the effect of improving the smoothness of the surface can be sufficiently obtained. On the other hand, when the content of the structure derived from a) or the a) component is 70% by mass or less with respect to the hard coat layer or the hard coat layer forming composition, the surface hardness can be sufficiently increased.

When the total solid content of the hard coat layer is set to 100% by mass, it is preferable to contain 18% to 50% by mass of the structure derived from a), and more preferably to contain 22% to 40% by mass of the source From the structure of a). When the total solid content of the composition for forming a hard coat layer is 100% by mass, it preferably contains 18% by mass to 50% by mass of component a), and more preferably contains 22% by mass to 40% by mass. a) Ingredients.

-b) Compounds having three or more groups containing ethylenically unsaturated double bonds 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 includes 25% by mass to 80% by mass of the structure derived from the following b).

b) A compound having three or more groups containing ethylenically unsaturated double bonds in the molecule.

In addition, it is preferable that the hard coat layer is formed by hardening a hard coat layer forming composition containing at least a), b), c), and d), and the total solid content of the hard coat layer forming composition is In the case of 100% by mass, the composition for forming a hard coat layer contains 25% by mass to 80% by mass of b).

The compound containing three or more groups containing ethylenically unsaturated double bonds in the molecule b) contained in the composition for forming a hard coat layer will be described. The compound in which b) has three or more groups containing an ethylenically unsaturated double bond in the molecule is also referred to as "b) component".

b) The component can express higher hardness by having three or more groups containing ethylenically unsaturated double bonds in the molecule.

As b) component, the ester of polyhydric alcohol and (meth)acrylic acid, vinylbenzene and its derivative(s), vinyl sulfide, (meth)acrylamide, etc. are mentioned.

Among them, from the viewpoint of hardness, a compound having three or more (meth)acrylic groups is preferable, and an acrylate compound that forms a hardened product with high hardness, which is widely used in the industry, is mentioned.

As such a compound, a compound which is an ester of a polyhydric alcohol and (meth)acrylic acid and which has three or more groups containing an ethylenically unsaturated double bond in a molecule|numerator is mentioned. For example, (two) pentaerythritol tetra(meth)acrylate, (two) pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide, EO) modified trimethylolpropane tri(meth)acrylate, propylene oxide (propylene oxide, PO) modified trimethylolpropane tri(meth)acrylate, EO modified tris(meth) phosphate Acrylate, trimethylolethane tri(meth)propylene Acid ester, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, (2) pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Pentaerythritol hexa(meth)acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, caprolactone modified Ethyl ethyl) isocyanurate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, 1,2,4-cyclohexanetetra(meth)acrylate, pentaglycerol triacrylate, etc.

Furthermore, resins (oligomers or prepolymers) having three or more (meth)acrylic groups, polyfunctional (meth)acrylates having three or more (meth)acrylic groups, and urethanes Ester (meth)acrylates are also preferred.

As resins (oligomers or prepolymers) having three or more (meth)acrylic groups, for example, polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, Alkyd resins, spiro acetal resins, polybutadiene resins, polythiol polyene resins, polyols and other polyfunctional compounds such as oligomers or prepolymers.

Specific examples of polyfunctional (meth)acrylates having three or more (meth)acryloyl groups include dipentaerythritol hexaacrylate (DPHA), etc. Japanese Patent Laid-Open No. 2007-256844, paragraph 0096 Exemplary compounds shown in.

Specific examples of multifunctional acrylate compounds having three or more (meth)acrylic groups include KAYARAD DPHA, DPHA-2C, PET-30, 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, large Esterified products of polyols and (meth)acrylic acid such as V#400 and V#36095D manufactured by Sakaji Chemical Industry Co., Ltd. In addition, UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, 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 Nippon Synthetic Chemical Co., Ltd.), UL-503LN (manufactured by Kyoeisha Chemical 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 ) UCB (manufactured by shares), Hi-Coap (Hi-Coap) AU-2010, AU-2020 (manufactured by Tokushiki (shares)), Aronix M-1960 (manufactured by Toakushiki Co., Ltd.) ), Art Resin (Art Resin) UN-3320HA, UN-3320HC, UN-3320HS, UN-904, HDP-4T and other trifunctional or more urethane acrylate compounds, Aronix M-8100 , M-8030, M-9050 (manufactured by Toagosei Co., Ltd.), KBM-8307 (manufactured by Daicel-Cytec (Co., Ltd.)) trifunctional or higher polyester compound, etc.

In addition, the b) component 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, 25% by mass to 80% by mass of the structure derived from b) is contained.

When the total solid content of the composition for forming a hard coat layer is 100% by mass, 25% by mass to 80% by mass of the b) component is contained. If the content of the structure derived from b) or the b) component is 25% by mass or more with respect to the hard coat layer or the hard coat layer forming composition, sufficient hardness can be obtained. On the other hand, when the content of the structure derived from b) or the component b) is 80% by mass or less with respect to the hard coat layer or the composition for forming a hard coat layer, it is due to the structure derived from a) or a ) The content of the component is reduced, so the smoothness is sufficient.

When the total solid content of the hard coat layer is set to 100% by mass, it is preferably 40% to 75% by mass of the structure derived from b), and more preferably 60% to 75% by mass of the source Structure from b). When the total solid content of the composition for forming a hard coat layer is 100% by mass, it preferably contains 40% to 75% by mass of component b), more preferably 60% to 75% by mass b) Ingredients.

-Other hardening compounds-

The composition for forming a hard coat layer may contain other curable compounds (hereinafter, also referred to as "other curable compounds") in addition to the a) component and b) component. As other curable compounds, various compounds having polymerizable groups that can be cured (polymerized) by curing treatment can be used. As the polymerizable group, a polymerizable group capable of undergoing a polymerization reaction by irradiation with light, electron beam or radiation, and a polymerizable group capable of undergoing a polymerization reaction by heating are mentioned, and a photopolymerizable group is preferred. In addition, other curable compounds may be monomers, oligomers, prepolymers, and the like.

Specific examples of the polymerizable group include polymerizable unsaturated groups such as (meth)acrylic acid groups, vinyl groups, styryl groups, and allyl groups, and ring openings such as epoxy groups. Polymeric polymerizable group. Among them, from the viewpoint of curability and the like, a (meth)acryloyl group is preferred.

As specific examples of other curable compounds that can be contained in the composition for forming a hard coat layer, the following compounds can be exemplified.

(Meth)acrylate diesters of alkanediols such as neopentyl glycol acrylate, 1,6-hexanediol (meth)acrylate, and propylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate (Meth)acrylic acid of polyoxyalkylene glycols such as acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. Diesters; (meth)acrylate diesters of polyhydric alcohols such as pentaerythritol di(meth)acrylate; 2,2-bis{4-(acryloxydiethoxy)phenyl}propane, 2, (Meth) acrylic diesters of ethylene oxide or propylene oxide adducts such as 2-bis{4-(acryloxypolypropoxy)phenyl}propane; urethane (meth) Acrylic esters; polyester (meth)acrylates; isocyanuric acrylates; epoxy (meth)acrylates.

Examples of urethane (meth)acrylates include, for example, reacting hydroxyl-containing compounds such as alcohols, polyols and/or hydroxyl-containing acrylates with isocyanates, or if necessary, using (meth)acrylic acid A urethane (meth)acrylate obtained by esterifying the polyurethane compound obtained by the reaction. As a specific example, various commercial products listed in paragraph 0017 of JP 2007-256844 A can be exemplified.

From the viewpoint of reducing curing shrinkage, the composition for forming a hard-coat layer may contain an epoxy-based compound having an epoxy group as a polymerizable group as another curing compound. As an epoxy compound, it is preferable to contain two or more rings in one molecule Multifunctional epoxy compound of oxy group. 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 Epoxy compounds described in 2005-140862, Japanese Patent Laid-Open No. 2005-140863, and Japanese Patent Laid-Open No. 2002-322430. In addition, it is also preferable to use a compound having both an epoxy group and an acrylic polymerizable group like glycidyl (meth)acrylate.

From the viewpoint of the hardness of the hard coat layer, when the total solid content of the hard coat layer forming composition is 100% by mass, it is relative to the total solid content of the hard coat layer forming composition The content of the other curable compound is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 1% by mass or less, still more preferably 0.01% by mass or less, and particularly preferably does not substantially contain other curable 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% by mass to 10% by mass of c) a radical polymerization initiator.

The c) radical polymerization initiator contained in the hard coat layer or the hard coat layer forming composition will be described. Hereinafter, the c) radical polymerization initiator is also referred to as "c) component".

The polymerization of the compound having an ethylenically unsaturated group can be performed by irradiating ionizing radiation or heating in the presence of a photo radical polymerization initiator or a thermal radical polymerization initiator.

As the photo- and thermal polymerization initiator, commercially available compounds can be used. The commercially available The compound is described in "Latest UV Curing Technology" (p.159, Issuer: Kazuhiro Takahashi, Issuer: Technology Information Association (Shares), issued in 1991) or Ciba Specialty Chemicals (Shares) In the product catalog.

As component c), specifically, alkyl phenone-based photopolymerization initiators (Irgacure 651, Irgacure 184, DAROCURE 1173, DAROCURE 1173, Irgacure 2959, Irgacure 127, Darocure MBF, Irgacure 907, Irgacure 369, Irgacure 379EG), Phosphine oxide series 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 hard coat layer forming composition is 100% by mass, the addition amount of component c) is in the range of 0.1% by mass to 10% by mass, preferably 1% by mass to 5% by mass, more preferably 2% to 4% by mass. When the total solid content of the hard coat layer or the hard coat layer forming composition is 100% by mass, c) When the addition amount of the component is 0.1% by mass or more, the polymerization proceeds sufficiently and the pencil of the hard coat layer can be improved hardness. On the other hand, when the total solid content of the hard coat layer or the hard coat layer forming composition is 100% by mass, when the addition amount of the c) component is 10% by mass or less, the UV light reaches the inside of the film and can be Improve the pencil hardness of the hard coat. These c) radical initiators can be used alone, or multiple types can be used in combination.

-d) Cationic polymerization initiator-

When the total solid content of the hard coat layer is set to 100% by mass, the present disclosure The hard coat layer contains 0.1% by mass to 10% by mass of d) cationic polymerization initiator.

The d) cationic polymerization initiator contained in the hard coat layer or the hard coat layer forming composition will be described. Hereinafter, d) cationic polymerization initiator is also referred to as "d) component".

As the component d), well-known acid generators such as photoinitiators for photocation polymerization, photodecolorizers of pigments, photochromic agents, or known acid generators used in micro resists, etc. can be cited Compounds and mixtures of these, etc.

For example, onium compounds, organic halogen compounds, and disulfite compounds can be cited. Specific examples of the organohalogen compound and the disulfite compound include the same compounds as described for the radical-generating compound.

Examples of the onium compound include diazonium salt, ammonium salt, imine salt, phosphonium salt, iodine salt, sulfonium salt, arsonium salt, selenium salt, etc., for example, the paragraph number of Japanese Patent Laid-Open No. 2002-29162 [0058] ] ~ The compound described in paragraph number [0059], etc.

In the present disclosure, examples of cationic polymerization initiators that can be used particularly suitably include onium salts. In terms of the sensitivity of the photopolymerization initiation and the stability of the raw materials of the compound, diazonium salts and iodonium salts are preferred. Among them, from the viewpoint of light resistance, the most preferred is the iodonium salt.

In the present disclosure, as specific examples of onium salts that can be suitably used, for example, the sulfonated sulfonate salt described in paragraph No. [0035] of Japanese Patent Laid-Open No. 9-268205, and Japanese Patent Special Paragraph No. [0010] to Paragraph No. [0011] of Kaikai No. 2000-71366, and Paragraph No. [0017] of Japanese Patent Laid-Open No. 2001-288205 Thiobenzyl The sulfonium salt of acid S-phenyl ester, the onium salt described in paragraph number [0030] to paragraph number [0033] of JP 2001-133696 A, and the like.

As other examples, the organometal/organic halide described in paragraph No. [0059] ~ paragraph No. [0062] of Japanese Patent Laid-Open No. 2002-29162, and the photo-protective group having an o-nitrobenzyl type can be cited. Compounds such as acid generators and compounds that generate sulfonic acid by photolysis (iminosulfonate etc.).

As specific compounds of the cationic polymerization initiator of the iodine salt series, B2380 (manufactured by Tokyo Chemical Industry), BBI-102 (manufactured by Midori Chemical), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), WPI-124 (manufactured by Wako Pure Chemical Industries, Ltd.) can be used. 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 the cationic polymerization initiator of the iodine salt type, the following compound FK-1 and compound FK-2 can be mentioned.

Photocationic polymerization initiator (Ibium salt compound) FK-1

Photocationic polymerization initiator (Ibium salt compound) FK-2

As d) component, only 1 type may be used, and 2 or more types may be used together.

When the total solid content of the hard coat layer or the hard coat layer forming composition is 100% by mass, the component d) is added in the range of 0.1% by mass to 10% by mass, preferably 0.5% by mass. It is added in the proportion of ~3.0% by mass. The addition amount in the above-mentioned range is preferable in terms of stability, polymerization reactivity, and the like of the curable composition.

-Other ingredients of hard coat-

In the hard coat layer, other components may be contained in addition to the components a) to d) which are preferable components.

-e) Inorganic particles reactive with epoxy groups or groups containing ethylenically unsaturated double bonds-

In the composition for forming a hard coat layer or a hard coat layer, it is preferable to add e) inorganic particles reactive with an epoxy group or a group containing an ethylenically unsaturated double bond. Hereinafter, e) inorganic particles having reactivity with an epoxy group or an ethylenically unsaturated double bond-containing group 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 the smoothness can be improved. Furthermore, by using inorganic particles reactive with an epoxy group or a group containing an ethylenically unsaturated double bond, the pencil hardness can be improved.

Examples of inorganic particles include silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, and aluminum oxide particles. Among them, e) 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 only mixing is performed, aggregates may be formed or the hard coat layer after hardening may easily crack. Therefore, in component e), in order to increase the affinity between the inorganic particles and the organic components, it is preferable to treat the surface of the inorganic particles with a surface modifier containing organic segments.

The surface modifier is preferably a surface modifier having a functional group capable of forming a bond with inorganic particles or capable of being adsorbed to inorganic particles and a functional group having affinity with organic components in the same molecule. As a surface modifier having a functional group that can be bonded or adsorbed to inorganic particles, metal alkoxide surface modifiers such as silane, aluminum, titanium, zirconium, etc. are preferred, or they have a phosphoric acid group, a sulfuric acid group, a sulfonic acid group, Surface modifier for anionic groups such as carboxylic acid groups. Furthermore, as the functional group having affinity with the organic component, it may be only a functional group that makes the hydrophilic and hydrophobic properties compatible with the organic component, but it is preferably a functional group that can chemically bond 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, the preferred surface modifiers of inorganic particles are metal alkoxides, or have anionic groups and ethylenically unsaturated double bonds in the same molecule. The hardening resin of the group or the ring-opening polymerizable group. By chemically bonding with organic components, the cross-linking density of the hard coat layer is increased, and the pencil hardness can be improved.

Representative examples of these surface modifiers include the following coupling agents containing unsaturated double bonds, organic curable resins containing phosphoric acid groups, organic curable resins containing sulfuric acid groups, and organic curable resins containing carboxylic acid groups. 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 hydrogen atom or CH ₃ )

The surface modification of these inorganic particles is preferably achieved in a solution. It can be the following method: when the inorganic particles are mechanically finely dispersed, the surface modifier is present together; or after the inorganic particles are finely dispersed, the surface modifier is added and stirred; or the surface is modified before the inorganic particles are finely dispersed (If necessary, heating and drying after heating, or changing the pH), and then finely dispersing. As a solution for dissolving the surface modifier, an organic solvent with high polarity is preferred. Specifically, known solvents such as alcohols, ketones, and esters can be cited.

Considering the balance between the hardness and brittleness of the coating film, the hard coat or hard coat When the total solid content of the forming composition is 100% by mass, the addition amount of the e) component is preferably 5% by mass to 40% by mass, and more preferably 10% by mass to 30% by mass.

The size (average primary particle size) of the inorganic particles is preferably 10 nm to 100 nm, more preferably 10 nm to 60 nm. The average particle size of the particles can be calculated from the electron micrograph. If the particle diameter of the inorganic particles is at least the lower limit value, the effect of improving the hardness can be obtained, and if the particle diameter is less than the upper limit value, 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, it is preferably non-spherical formed by connecting 2 to 10 inorganic particles. It is estimated that the hardness is improved by forming a strong particle network structure by using inorganic particles in which a plurality of inorganic particles are connected in a chain shape.

Specific examples of inorganic particles include: ELECOM V-8802 (spherical silicon dioxide particles with an average primary particle diameter of 12 nm manufactured by Nippon Chemicals Co., Ltd.), ELECOM V-8803 (Special-shaped silicon dioxide particles manufactured by Nissan Chemical Co., Ltd.), MiBK-SD (spherical silicon dioxide particles with an average primary particle size of 10nm to 20nm manufactured by Nissan Chemical Industry Co., Ltd.), MEK-AC-2140Z (Nissan Chemical Industry Co., Ltd.) Spherical silica particles with an average primary particle size of 10nm~20nm manufactured by Kogyo Co., Ltd.), MEK-AC-4130 (Spherical silica particles with an average primary particle size of 40nm~50nm manufactured by Nissan Chemical Industry Co., Ltd.) ), MiBK-SD-L (Spherical silicon dioxide particles with an average primary particle size of 40nm-50nm manufactured by Nissan Chemical Industry Co., Ltd.), MEK-AC-5140Z (Average primary particle size manufactured by Nissan Chemical Industry Co., Ltd. It is 70nm~100nm spherical silicon dioxide particles) and so on. Among them, from the viewpoint of imparting hardness to the surface, it is preferable to use irregular shapes. ELECOM V-8803.

-f) Polyester urethane-

In the hard coat layer or the hard coat layer forming composition 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".

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. It is considered that a polyester urethane having a tensile strength of 25 MPa or more and a tensile elongation of 200% or more contributes to the increase in hardness of the hard coat layer and imparts moderate flexibility. It is estimated that this will contribute to the increase in hardness and brittleness of the hard coating layer.

In addition, if the polyester urethane content with respect to 100 parts by mass of the total solid content of the hard coat layer or the hard coat layer forming composition is 1 part by mass or more, it can be sufficiently obtained by adding polyester If the effect of the urethane is 10 parts by mass or less, the hardness of the hardened layer can be maintained. Therefore, the polyester urethane content with respect to 100 parts by mass of the total solid content of the hard coat layer or the hard coat layer forming composition is set to a range of 1 part by mass to 10 parts by mass. From the viewpoint of improving brittleness and suppressing decrease in 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.

In the case of using polyester urethane exhibiting the tensile strength and tensile elongation as the polyester urethane, moderate softness is imparted to the hard coat layer It also contributes to achieving both high hardness and brittleness improvement. The tensile strength is more preferably 40 MPa or more, and still more preferably 50 MPa or more. In addition, 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, more preferably 600% or more. In addition, from the viewpoint of ensuring pencil hardness, which is one of the indexes of film hardness, the tensile elongation is preferably 1000% or less. The measuring method of pencil hardness will be described later with respect to Examples. The tensile strength and tensile elongation of the polyester urethane are the values measured using a tensile strength tester in accordance with JIS K 6251.

Polyester urethane can be obtained by polymerization of monomer components including at least a diol, a dicarboxylic acid, and a diisocyanate. As the aforementioned three kinds of monomers, a polyester urethane 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 alkenylene group, an alkynylene group, an arylene group, or a combination of these.

The alkylene group, alkenylene group, and alkynylene group preferably have a linear structure.

When the hydrocarbon group is an alkylene group, an alkenylene group, or an alkynylene group, the number of carbon atoms is preferably 1-8, more preferably 2-6, and even more preferably 2-4.

The arylene group may have an alkyl group having 1 to 8 carbon atoms as a substituent.

As the arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and p-phenylene is still more preferred.

As the hydrocarbon group, the alkylene group, the arylene group, or a combination of these are particularly preferred.

The diol used as the monomer of the polyester urethane is preferably ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 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.

As the diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate are preferred. ,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 5000 or more, more preferably 10000 or more, and from the viewpoint of compatibility with the curable compound In other words, it is preferably 50,000 or less.

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

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

-g) Antifouling agent-

When g) an antifouling agent is contained in the hard coat layer or the hard coat layer forming composition of the present disclosure, the adhesion of fingerprints and stains is reduced, and the wiping of the attached stains becomes simple and preferable. In addition, it is also preferable from the viewpoint of improving the scratch resistance by improving the smoothness of the surface. Hereinafter, g) antifouling agent is also referred to as "g) component".

The hard coat layer of the present disclosure is preferably: g) the antifouling agent contains a fluorine-containing compound, the fluorine-containing compound contained has a perfluoropolyether group and a polymerizable unsaturated group, and has multiple polymerizable unsaturated groups in one molecule. Saturated base.

The g) antifouling agent that can be used in the present disclosure will be described.

[Fluorine-containing compound with polymerizable unsaturated group]

For g) the antifouling agent contains a fluorine-containing compound, and the fluorine-containing compound contained is a compound having a perfluoropolyether group and a polymerizable unsaturated group and having multiple polymerizable unsaturated groups in one molecule (hereinafter, also referred to as The case of "fluorine-containing antifouling agent") will be explained.

The fluorine-containing antifouling agent preferably contains a fluorine-based compound having a structure represented by the following formula (F).

Formula (F): (Rf)-[(W)-(R _A ) _n ] _m

Formula, Rf represents a (per) fluoroalkyl or (per) fluoropolyether group, W represents a linking group, R _A represents a polymerizable unsaturated group. n represents an integer from 1 to 3. m represents an integer from 1 to 3.

It is thought that the fluorine-containing antifouling agent has the following effects (1) to (3) by having a polymerizable unsaturated group.

(1) The solubility in organic solvents and the compatibility with compounds having unsaturated double bonds and the like are improved. Therefore, it is considered that the antifouling agent does not form agglomerates and can be uniformly localized on the surface. In addition, defects caused by aggregates can be prevented.

(2) Even if the fluorine-containing antifouling agent is locally present on the surface, the fluorine-containing antifouling agent can form a covalent bond with each other or with a compound having an unsaturated double bond by photopolymerization, so that it can prevent the abrasion caused Peeling of antifouling agent and deterioration of antifouling properties.

(3) It can prevent the loss of antifouling property and the deterioration of appearance caused by the exudation and precipitation of the antifouling agent.

In the formula (F), R _A represents a polymerizable unsaturated group. The polymerizable unsaturated group is not particularly limited as long as it is a group that can cause a radical polymerization reaction by irradiating active energy rays such as ultraviolet rays or electron beams, and examples thereof include (meth)acrylic acid groups and (meth)acrylic acid groups Group, vinyl group, allyl group, etc., (meth)acryloyloxy group, (meth)acryloyloxy group, and any hydrogen atom in these groups are substituted with fluorine atom base.

As a specific example of a polymerizable unsaturated group, the group which has a structure shown below is preferable.

[化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 preferable that the fluorine content in Rf is high.

The (per)fluoroalkyl group is preferably a group having 1 to 20 carbons, and more preferably a group having 1 to 10 carbons.

The (per)fluoroalkyl group can be straight chain (e.g. -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. ) May also be an alicyclic structure (preferably a 5-membered ring or a 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 it may be a monovalent group or a group having a valence of two or more. As the fluoropolyether group, 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, a C 4-20 fluorocycloalkyl group having 4 or more fluorine atoms, etc. In addition, 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 -, etc.

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 fluorine-containing antifouling agent particularly preferably has a perfluoropolyether group represented _{by -(CF 2} O) _p -(CF ₂ CF ₂ O) _{q -.}

Said p and q each independently represent an integer of 0-20. Here, p+q is an integer of 1 or more.

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

In formula (F), W represents a linking group. Examples of W include an alkylene group, an arylene group, a heteroalkylene group, or a linking group formed by combining these. These linking groups may further have an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamido group, etc. or the These combinations of functional groups.

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 (1) to (3) can be obtained more remarkably, in formula (F), the product of n and m (n×m) is preferably 2 or more, more preferably 4 above.

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

Formula ^{(F-1): Rf 2} (CF 2 CF 2) p R '2 CH 2 CH 2 R 2 OCOCR 1 = CH 2

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

To R ^'2 represents a case where the divalent linking group, a divalent linking group, the linking group include the same W.

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

Although the specific example of the compound represented by Formula (F-1) is shown below, it is not limited to these compounds.

[化8]

If the compound represented by the formula (F-1) is synthesized using short-chain polymerization, it may include the group Rf ^{2 of the formula (F-1) according to the conditions of the short-chain polymerization and the separation conditions of the reaction mixture.} a plurality of fluorine _{(CF 2 CF 2) p R} '2 CH 2 CH 2 R 2 O- are p-k, k + 1, k + 2, ... , etc. (meth) acrylates.

Formula (F-2): F(CF ₂ ) _q -CH ₂ -CHX-CH ₂ Y

In formula (F-2), q is an integer from 1 to 20, X and Y are each independently any one of (meth)acryloxy or hydroxy, and at least one of them is (meth)acryl基oxy。

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 end, and the fluorine-containing (methyl)} Even a small amount of acrylate can effectively align the trifluoromethyl group on the surface.

In terms of antifouling properties and ease of manufacture, q is preferably 6-20, more preferably 8-10. The fluorine-containing (meth)acrylate having a fluoroalkyl group having 8 to 10 carbon atoms exhibits excellent water and oil repellency compared to fluorine-containing (meth)acrylate having a fluoroalkyl group with other chain lengths. Therefore, the antifouling property is excellent.

Specific examples of the fluorine-containing (meth)acrylate represented by the formula (F-2) include: 1-(meth)acryloyloxy-2-hydroxy-4,4,5,5, 6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-Ecosylfluorotridecane, 2-(meth)acrylic acid Baseoxy-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 fluorotridecane and 1,2-bis(meth)acryloyloxy 4,4,5,5,6,6,7,7,8,8,9,9,10,10, 11,11,12,12,13,13,13-Ecosone fluorotridecane and so on. In the present disclosure, it is preferably 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-Eicosanfluorotridecane.

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, s is an integer of 1-20, and r represents an integer of 1-4.

Fluorine atom-containing monofunctional (meth)propylene represented by the formula (F-3) The acid ester can be obtained by reacting a (meth)acrylic acid halide with a fluorine atom-containing alcohol compound represented by the following formula (FG-3).

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 of 1-20, and r represents an integer of 1-4.

As a specific example of the fluorine atom-containing alcohol compound represented by the formula (FG-3), for example, 1H,1H-perfluoro-3,6-dioxaheptan-1-ol, 1H,1H- Perfluoro-3,6-dioxaoctan-1-ol, 1H,1H-perfluoro-3,6-dioxadecan-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-trioxa Heterotridecane-1-ol, 1H,1H-perfluoro-3,6,9,12-tetraoxetridecan-1-ol, 1H,1H-perfluoro-3,6,9,12- Tetraoxatetradecane-1-ol, 1H,1H-perfluoro-3,6,9,12-tetraoxahexadecane-1-ol, 1H,1H-perfluoro-3,6,9, 12,15-pentaoxahexadecane-1-ol, 1H,1H-perfluoro-3,6,9,12,15-pentaoxahexadecane-1-ol, 1H,1H-perfluoro- 3,6,9,12,15-pentaoxanonadecan-1-ol, 1H,1H-perfluoro-3,6,9,12,15,18-hexaoxaicosan-1-ol , 1H,1H-perfluoro-3,6,9,12,15,18-hexaoxadocosan-1-ol, 1H,1H-perfluoro-3,6,9,12,15,18 ,21-Heptaoxatricosane-1-ol, 1H,1H-perfluoro-3,6,9,12,15,18,21-heptaoxapentacosan-1-ol, etc.

These compounds are available on the market. As specific examples thereof, for example, 1H,1H-perfluoro-3,6-dioxaheptan-1-ol (trade name "C5GOL", Exfluor (Exfluor ) Manufactured by the company), 1H,1H-perfluoro-3,6,9-trioxadecane-1-ol (trade name "C7GOL", manufactured by Exfluor), 1H,1H-full Fluorine-3,6- Dioxadecan-1-ol (trade name "C8GOL", manufactured by Exfluor), 1H,1H-perfluoro-3,6,9-trioxadecan-1-ol (Trade name "C10GOL", manufactured by Exfluor), 1H,1H-perfluoro-3,6,9,12-tetraoxahexadecane-1-ol (trade name "C12GOL", Exfluor (manufactured by Exfluor), etc.

In the present disclosure, 1H,1H-perfluoro-3,6,9,12-tetraoxetridecan-1-ol is preferably used.

In addition, examples of the (meth)acrylic halides that react with the fluorine atom-containing alcohol compound represented by the formula (FG-3) include (meth)acrylic fluoride, (meth)acrylic chloride, ( (Meth)acrylic bromide, (meth)acrylic iodine. From the standpoint of easy availability, etc., (meth)acrylic acid chloride is preferred.

Preferred specific examples of the compound represented by formula (F-3) are shown below, but are not limited to these specific examples. Furthermore, 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, a compound represented by the following formula (F-3A) may 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 ]

(In the formula, X ¹ and X ² each independently represent 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 represents 0 or 1, Rf ³ represents a fluorinated alkyl group containing an ether bond with a carbon number of 18 to 200), and ^{has 6 or more in the Rf 3} group, which is represented by the formula (FG-3A): -(CX ⁶ ₂ CF ₂ CF ₂ O)-

(In the formula, X ⁶ is F or H) a fluorine-containing unsaturated compound of a repeating unit represented by.

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, preferably a group having the following structure. The definition of each symbol in (c-1) to (c-3) has the same meaning as in formula (FG-3A).

[化9]

In addition, the fluorine-containing polyether compound represented by formula (F-3A) may have a plurality of polymerizable unsaturated groups, and structures such as the structures shown below are preferably cited.

[化10]

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

In the fluorine-containing polyether compound represented by the formula (F-3A), with regard to the Rf ³ group, it is important that the fluorine-containing polyether chain of the formula (FG-3A) contains 6 ^{in the form of a repeating unit in Rf 3} As described above, antifouling properties can be imparted by this.

In addition, in more detail, it may also be a mixture of compounds containing 6 or more repeating units of the fluorine-containing polyether chain, but when used in the form of a mixture, it is preferably set as the following mixture: in the repeating unit In the distribution of fluorine-containing unsaturated compounds with less than 6 fluorine-containing unsaturated compounds and fluorine-containing unsaturated compounds with 6 or more repeating units, the presence ratio of fluorine-containing unsaturated compounds with 6 or more repeating units of the polyether chain is the 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 stain resistance can be improved, especially the removability of stains containing oil components. In addition, air permeability can also be imparted more effectively. In addition, the fluorine-containing polyether chain may be located at ^{the end of the Rf 3} group, or may exist 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-

(In the formula, X ^{6 is the} same as the formula (FG-3A), R ⁴ represents a hydrogen atom, a halogen atom or selected from 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 R ⁵ represents an organic group having a valence of two or more, 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 that 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 the fluorine-containing polyether chain of formula (FG-3A) to a reactive carbon-carbon double bond. For example, it can be selected from an alkylene group, a fluorine-containing alkylene group, an ether bond-containing alkylene group, and an ether bond-containing fluorinated alkylene group. Among them, in terms of transparency and low refractive index, a fluorinated alkylene group and a fluorinated alkylene group containing an ether bond are preferred.

As a specific example of the fluorine-containing polyether compound represented by formula (F-3A), the compounds listed in WO2003/022906 pamphlet and the like can be preferably used. In the present 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 equal to 1 at the same time, the formula (F-4) and the formula (F-5) can be cited as the following preferred aspects.

Formula (F-4): (Rf ¹ )-[(W)-(R _A ) _n ] _m

(In the formula (F-4), Rf ¹ represents a (per) fluoroalkyl or (per) fluoropolyether group, W represents a linking group, R _A represents an unsaturated double bond with a functional group represented by 1 to 3 .n Integer, m represents an integer from 1 to 3, when n is different from m, it is 1)

From the viewpoint of excellent water and oil repellency and excellent continuity (anti-fouling durability) of water and oil repellency, n is preferably 2 to 3 and m is 1 to 3, and more preferably n is 2 to 3, m It is 2~3, the best is n is 3, m is 2~3.

Rf ¹ can use monovalent to trivalent radicals. When Rf ¹ is monovalent, the terminal group is preferably (C _n F _2n+1 )-, (C _n F _2n+1 O)-, (XC _n F _2n O)-, (XC _n F _2n+1 )-(In the formula, X is hydrogen, chlorine or bromine, and n is an integer of 1-10). _{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 )-, etc.

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

When 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 )-etc.

Here, the average value of q, r, and s in the formula is 0-50. Preferably it is 3-30, more preferably 3-20, most preferably 4-15. t is an integer from 2 to 6.

Preferred specific examples or synthesis methods of the compound represented by formula (F-4) are described in International Publication No. 2005/113690.

Hereinafter, the compound whose average value of p in F(CF(CF ₃ )CF ₂ O) _p CF(CF ₃ )- is 6-7 is described as "HFPO-", and -(CF(CF ₃ )CF ₂ O ) _{Compounds in which the average value of p is 6-7 in p} CF(CF ₃ )- 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 the compound represented by the formula (F-4), a compound represented by the following formula (F-5) can also be used.

Formula (F-5): CH ₂ =CX ₁ -COO-CHY-CH ₂ -OCO-CX ₂ =CH ₂

(In the formula, X ₁ and X ₂ each independently represent a hydrogen atom or a methyl group, and Y represents a fluoroalkyl group with 3 or more fluorine atoms and a carbon number of 2 to 20 or a C 4-20 group with 4 or more fluorine atoms. Fluorocycloalkyl)

In the present disclosure, the compound in which the polymerizable unsaturated group is a (meth)acryloxy group may have a plurality of (meth)acryloxy groups. With fluorine-containing antifouling agent, it has multiple The (meth)acryloyloxy group exhibits a three-dimensional mesh structure when it is cured, the glass transition temperature is high, the transferability of the antifouling agent is low, and the durability against repeated erasure of stains can be improved. Furthermore, a cured film excellent in heat resistance, weather resistance, etc. can be obtained.

As specific examples of the compound represented by the formula (F-5), for example, di(meth)acrylic acid-2,2,2-trifluoroethylglycol, di(meth)acrylic acid- 2,2,3,3,3-Pentafluoropropyl glycol, di(meth)acrylic acid-2,2,3,3,4,4,4-heptafluorobutyl glycol, di(meth) Base) 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-Undecafluorohexyl 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-pentafluorooctane Ethylene glycol, di(meth)acrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl glycol, bis(meth)acrylic acid Base) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl glycol, bis(methyl Base) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonafluorodecyl glycol , Di(meth)acrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl glycol , Di(meth)acrylic acid-2-trifluoromethyl-3,3,3-trifluoropropyl glycol, di(meth)acrylic acid-3-trifluoromethyl-4,4,4-tri Fluorobutyl glycol, di(meth)acrylic acid-1-methyl-2,2,3,3,3-pentafluoropropyl glycol, di(meth)acrylic acid-1-methyl-2 ,2,3,3,4,4,4-heptafluorobutyl glycol, etc., when used, can be used alone or as a mixture. When preparing such a di(meth)acrylate, it can manufacture by a well-known method as listed in Japanese Patent Laid-Open No. 6-306326. In the present disclosure, diacrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoride can be preferably used Nonyl glycol.

In the present disclosure, the compound in which the polymerizable unsaturated group is a (meth)acryloxy 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 of monomers, oligomers, or polymers.

The fluorine-containing antifouling agent preferably further has a substituent that contributes to bond formation or compatibility in the hard coat film. The substituents may be the same or different, and preferably have a plurality of them. Examples of preferable substituents include: acryloyl, methacryloyl, vinyl, allyl, cinnamyl, epoxy, oxetanyl, hydroxy, and polyoxyalkylene. , Carboxyl, amine, etc.

The fluorine-containing antifouling agent may be a polymer with a compound not containing fluorine atoms, or may be an oligomer.

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

When the fluorine-containing compound contains a silicone 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

(Wherein, R is a hydrogen atom, a methyl, ethyl, propyl or phenyl group, R ^F is an organic group containing a fluorine atom, 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 the compound industrially, and if it is 1.75 or less, it is easy to have both curability 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 And the group in which arbitrary hydrogen atoms in these groups are substituted with fluorine atoms.

In the case where the fluorine-containing compound contains a siloxane structure, a preferred example of the siloxane structure is the terminal and/or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units In the structure with substituents. The compound chain containing a dimethylsilyloxy group as a repeating unit may also contain structural units other than the dimethylsilyloxy group. The substituents may be the same or different, and it is preferable to have a plurality of them. Examples of preferred substituents include (meth)acryloyl groups, (meth)acryloyloxy groups, vinyl groups, allyl groups, cinnamyl groups, epoxy groups, and oxetanyl groups. Among the groups such as hydroxy, fluoroalkyl, polyoxyalkylene, carboxyl, amine, etc., particularly from the viewpoint of suppressing the bleeding of the antifouling agent, a (meth)acryloxy group is preferred. In addition, as the number of substituents, from the viewpoint of improving the biased existence of the antifouling agent and suppressing the exudation of the antifouling agent, it is preferably 1500 g in terms of functional group equivalent. mol ^-1 ~20000g. mol ^-1 .

R ^f is an organic group containing a fluorine atom, preferably a group represented by C _x F _2x+1 (CH ₂ ) _p- (where x is an integer from 1 to 8 and p is an integer from 2 to 10) Or alkyl substituted by 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 a (meth) acrylic group-containing organic group, in terms of easiness to synthesize on an industrial, and more preferably is Si atom bond Si-OC bond. C is preferably 0.4 to 0.8, more preferably 0.6 to 0.8. If c is 0.4 or more, the curability is improved, and if it is 0.8 or less, the antifouling property is improved.

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

When the fluorine-containing compound contains a silicone structure, the fluorine-containing compound preferably contains 3 or more F atoms and 3 or more Si atoms in one molecule, preferably 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, it can promote the existence of deviation toward the surface, and the antifouling property is sufficient.

When the fluorine-containing compound contains a siloxane structure, the fluorine-containing compound can be produced using a known method listed in JP 2007-145884 A, etc.

When the fluorine-containing compound contains a siloxane structure, the siloxane structure may be any one of linear, branched, and cyclic. Among these, compounds having a branched or cyclic structure are especially It is preferable because it has good compatibility with a compound having an unsaturated double bond described later, does not shrink, and tends to cause deviation toward the surface. Here, as the compound whose siloxane structure is branched, 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

(Wherein, R, R ^f, R ^A as defined above, m = 0,1 or 2, in particular m = 2, k = 0 or 1)

In addition, as a compound whose siloxane structure is a cyclic structure, a compound represented by the following formula (F-8) is preferred.

Formula ^{(F-8) :( R f} RSiO) (R A RSiO) n ( wherein, R, R ^f, R ^A as defined above, n ≧ 2, in particular 3 ≦ n ≦ 5)

As a specific example of such a fluorine-containing polysiloxane compound, the following compounds etc. are mentioned.

[化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 5000, more preferably 1000 or more and less than 5000, and More preferably, it is 1,000 or more and less than 3500. If Mw is 400 or more, the surface mobility of the antifouling agent becomes high, which is preferable. In addition, if the Mw is less than 5000, the surface mobility of the fluorine-containing antifouling agent is not hindered from the application to the curing step, and it is easy to align uniformly on the surface of the hard coat layer. Therefore, the antifouling property and film hardness are improved. Better.

Among them, when 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 amount of the fluorine-containing antifouling agent added is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, relative to the total solid content in the hard coat layer or the composition for forming the hard coat layer. More preferably, it is 1% by mass to 10% by mass. If the addition 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 hard coat layer forming composition, the proportion of the antifouling agent having water and oil repellency is moderate, and it can Obtain sufficient antifouling properties. In addition, if the addition amount of the fluorine-containing antifouling agent is 20% by mass or less relative to the total solid content in the hard coat layer or the hard coat layer forming composition, the antifouling agent that cannot be mixed with the resin component will not precipitate To the surface, film whitening or white powder will not occur on the surface, so it is preferred.

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

As an example of a preferable fluorine-containing antifouling agent, R-2020, M-2020, R-3833, M-3833, Optool DAC ( The above is the trade name), manufactured by DIC Megafac (registered trademark) F-171, F-172, F-179A, Defensa (Defensa) MCF-300, MCF-323 (the above are trade names), etc., but not limited to these example.

[Polysiloxane compound with a polymerizable unsaturated group and a weight average molecular weight of 15,000 or more]

Next, a polysiloxane compound having a polymerizable unsaturated group and having a weight average molecular weight of 15,000 or more, which can be used as the component g), will be described. In addition, the polysiloxane compound having a molecular weight of 15,000 or more is referred to as a "polysiloxane antifouling agent" below.

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

As a preferable example of a polysiloxane antifouling agent, the compound which has a substituent in the terminal and/or side chain of a compound chain containing a some dimethylsilyloxy unit as a repeating unit is mentioned.

The compound chain containing a dimethylsilyloxy group as a repeating unit may also contain structural units other than the dimethylsilyloxy group. The substituents may be the same or different, and it is preferable to have a plurality of them. Examples of preferred substituents include (meth)acryloyl groups, (meth)acryloyloxy groups, vinyl groups, allyl groups, cinnamyl groups, epoxy groups, and oxetanyl groups. Among the groups such as hydroxy, fluoroalkyl, polyoxyalkylene, carboxyl, amine, etc., particularly from the viewpoint of suppressing the bleeding of the antifouling agent, a (meth)acryloxy group is preferred. In addition, as the number of substituents, from the viewpoint of improving the biased existence of the antifouling agent and suppressing the exudation of the antifouling agent, it is preferably 1500 g in terms of functional group equivalent. mol ^-1 ~20000g. mol ^-1 .

The polysiloxane antifouling agent is preferably a compound containing 3 or more F atoms and 3 or more Si atoms in one molecule, 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, it can promote the existence of deviation toward the surface, and the antifouling property is sufficient.

The polysiloxane antifouling agent can be produced using a known method listed in JP 2007-145884 A, etc.

As an additive with a polysiloxane structure, a reactive group-containing polysiloxane {e.g. "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" (product name ), the above is manufactured by Shin-Etsu Chemical Industry (Stock); "AK-5", "AK-30", "AK-32" (trade name), the above is manufactured by Toagosei (Stock); "Silaplane )FM0725", "SilaplaneFM0721" (trade name), the above are manufactured by Chisso (Stock); "DMS-U22", "RMS-033", "UMS-182" (commodity Name), the above is made by Gelest, etc.} is also preferred. In addition, the silicone-based compounds described in Table 2 or Table 3 of JP 2003-112383 A can also be preferably used.

As the silicone structure contained in the polysiloxane antifouling agent, it may be linear, branched, or cyclic. Among these, compounds having a branched or cyclic structure are combined with The compound having an unsaturated double bond described later has good compatibility, no shrinkage, and tends to cause deviation toward the surface, which is preferable.

The weight average molecular weight of the polysiloxane antifouling agent is 15000 or more, preferably It is 15,000 or more and 50,000 or less, 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, the presence of the surface bias of the polysiloxane is reduced, resulting in deterioration of antifouling properties and a decrease in hardness, which is not preferable from this point of view. However, when the fluorine-containing compound having a polymerizable unsaturated group has a polysiloxane structure, the above-mentioned problem is not caused.

The weight average molecular weight of the polysiloxane antifouling agent can be measured using a molecular exclusion chromatography method such as 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, more preferably 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 And it is less than 20% by mass, more preferably 1% by mass or more and less than 15% by mass, most preferably 1% by mass or more and less than 10% by mass. If the addition amount of the polysiloxane antifouling agent is 1% by mass or more relative to the total solid content in the hard coat layer or the hard coat layer forming composition, the proportion of the antifouling agent having water and oil repellency is moderate , Can obtain sufficient anti-fouling properties. In addition, if the addition amount of the polysiloxane antifouling agent is less than 25% by mass relative to the total solid content in the hard coat layer or the hard coat layer forming composition, the antifouling agent that cannot be mixed with the resin component is not It will precipitate to the surface and will not whiten the film or produce white powder on the surface, so it is preferred.

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 thickness direction The above distribution state is preferably to satisfy 51%<X/Y<100%. When X/Y is greater than 51%, the antifouling agent will not be distributed inside the film of the hard coat layer, which is preferable in terms of antifouling properties and film hardness. Furthermore, the so-called surface vicinity refers to an area less than 1 μm deep from the surface of the hard coat layer, which can be obtained by using time-of-flight secondary ion mass spectrometry (TOF-SIMS) The ratio of the measured F ^- fragment or Si ₂ C ₅ H ₁₅ O ^{+ fragment is measured.}

g) The antifouling agent is preferably an antifouling agent that is dissolved in a liquid or solvent at 20°C. The solvent can be appropriately selected according to the polarity of the compound, and an organic solvent mixed with dimethyl carbonate is preferred, and aliphatic or aromatic alcohols, ketones, esters, and ether solvents are exemplified. It is particularly good if it is dissolved in dimethyl carbonate.

Regarding g) 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 still 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.

(Measurement method of surface tension of antifouling agent)

The antifouling agent was spin-coated on the quartz substrate, and dried in the presence of a solvent to produce a film. Then, using a contact angle meter ["CA-X" contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.], in a dry state (20℃/65%RH), pure water is used as a liquid to form a diameter on the tip of the needle A drop of 1.0 mm is brought into contact with the surface of the spin-coated film to form a drop on the film. The angle of the side containing the liquid among the angles formed by the tangent line to the surface of the liquid and the surface of the film at the point where the film and the liquid are in contact is used as the contact angle. In addition, instead of water, diiodomethane was used to measure the contact angle, and the surface free energy was obtained by the following equation.

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 (Journal of Applied Polymer Science, J.Appl.Polym.Sci.,) 13,1741 (1969) as a reference, based on pure water experimentally determined on an anti-reflection film The contact angles θ _H2O and θ _{CH2I2 of} H ₂ O and diiodomethane CH ₂ I ₂ are calculated 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 g) antifouling agent described above, a compound synthesized by a known method can be used, or a commercially available product can also 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, if it can dissolve or disperse each component; it is easy to form a uniform surface texture in the coating step and the drying step; it can ensure liquid storage; it has a moderate saturated vapor pressure and other viewpoints. Various solvents can be used .

Two or more solvents can be mixed and used as the solvent. In particular, from the viewpoint of drying load, it is preferable to contain a solvent having a boiling point of 100°C or less at normal pressure and room temperature as the main component, and to adjust the drying rate to contain a solvent having a boiling point of more than 100°C in a small amount.

The composition for forming a hard coat layer preferably contains 30% to 80% by mass of all solvents of the coating composition, and a solvent having a boiling point of 80° C. or less, and more preferably contains 50% to 70% by mass . By setting the solvent ratio with a boiling point of 80° C. or lower to the above ratio, it is possible to moderately suppress the infiltration of the resin component into the polyester film. In addition, the viscosity increase rate during drying is increased, thereby suppressing particle sedimentation.

Listed below are solvents with a boiling point of 100°C or less. In addition, the temperature described together is the boiling point of each solvent.

As a solvent with a boiling point of 100°C or less, there are, for example, hydrocarbons such as hexane (68.7°C), heptane (98.4°C), cyclohexane (80.7°C), benzene (80.1°C), dichloromethane (39.8°C) , Chloroform (61.2℃), carbon tetrachloride (76.8℃), 1,2-dichloroethane (83.5℃), trichloroethylene (87.2℃) and other halogenated hydrocarbons, diethyl ether (34.6℃), Diisopropyl ether (68.5℃), dipropyl ether (90.5℃), tetrahydrofuran (66℃) and other ethers, ethyl formate (54.2℃), methyl acetate (57.8℃), ethyl acetate (77.1℃) ), esters such as isopropyl acetate (89°C), ketones such as acetone (56.1°C), 2-butanone (methyl ethyl ketone: hereafter sometimes referred to as MEK, 79.6°C), methanol (64.5°C) , Ethanol (78.3℃), 2-propanol (82.4℃), 1-propanol (97.2℃) and other alcohols, acetonitrile (81.6℃), propionitrile (97.4℃) and other cyano compounds, carbon disulfide (46.2℃) Wait. Among them, ketones and esters are preferred, and ketones are particularly preferred. Among ketones, 2-butanone is particularly preferred.

Examples of solvents with 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°C). ℃), dibutyl ether (142.4℃), isobutyl acetate (118℃), cyclohexanone (155.7℃), 2-methyl-4-pentanone (methyl isobutyl ketone): It is called MIBK, 115.9℃), 1-butanol (117.7℃), N,N-dimethylformamide (153℃), N,N-dimethylacetamide (166℃), dimethyl Kiya 碸 (189℃) and so on. Preferred are cyclohexanone and 2-methyl-4-pentanone.

(Surfactant)

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

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

As a preferable example of the fluorine-based surfactant, for example, a copolymer of a fluorine-containing aliphatic group (hereinafter, also abbreviated as "fluorine-based polymer") can be cited. For the fluorine-based polymer, useful are Acrylic resin and methacrylic acid containing repeating units corresponding to monomers (i) below or repeating units corresponding to monomers (i) and further including repeating units corresponding to monomers (ii) below Resins and copolymers with vinyl monomers copolymerizable with them.

(i) Fluorine-containing aliphatic group monomer represented by the following formula (i-1)

Formula (i-1) [化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 preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(ii) The monomer represented by the following formula (ii-1) which can be copolymerized with the (i)

Formula (ii-1)

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 with 1 to 4 carbon atoms, specifically It is a methyl group, an ethyl group, a propyl group, a butyl group, Preferably it is a hydrogen atom or a methyl group. Y is preferably an oxygen atom, -N(H)- and -N(CH ₃ )-.

R ¹⁴ represents an optionally substituted linear, branched or cyclic alkyl group having 4 or more and 20 or less carbon atoms. Examples of the substituent of the alkyl group of R ¹⁴ include a hydroxyl group, an alkyl carbonyl group, an aryl carbonyl 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 cyano group. Group, amino group, etc., but not limited to these. As the linear, branched or cyclic alkyl group having 4 or more and 20 or less carbon atoms, linear and branchable butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, eicosyl, etc., as well as monocyclic cycloalkyls such as cyclohexyl, cycloheptyl, bicycloheptyl, and bicyclodecyl , Tricycloundecyl, tetracyclododecyl, adamantyl, norbornyl, tetracyclodecyl and other polycyclic cycloalkyls.

The amount of the fluorinated 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 , Preferably in the range of 15 mol% to 70 mol%, more preferably 20 mol% to 60 mol%.

The preferred mass average molecular weight of the fluorine-based polymer is preferably 3000 to 100,000, more preferably 5,000 to 80,000. Furthermore, with respect to 100 parts by mass of the coating liquid, the preferred addition amount of the fluorine-based polymer is in the range of 0.001 parts by mass to 5 parts by mass, more preferably in the range of 0.005 parts by mass to 3 parts by mass, and more preferably 0.01 parts by mass ~1 part by mass. If the amount of fluorine-based polymer added is 0.001 parts by mass or more, the effect of adding the fluorine-based polymer can be fully obtained, and if it is 5 parts by mass or less, the following problem will not occur: the drying of the coating film is not fully performed , Or adversely affect the performance of the coating film.

As an example of a preferable silicone compound, Shin-Etsu Chemical Industry (Stock) X-22-174DX, X-22-2426, X22-164C, X-22-176D (the above are trade names) manufactured by (Stock); FM-7725, FM-5521 manufactured by Chisso (Stock) , FM-6621 (the above are the trade names); DMS-U22, RMS-033 (the above are the trade names) manufactured by Gelest; Toray. SH200, DC11PA, ST80PA, FZ-2105, L-7604, Y-7006, SS-2801 (the above are trade names) manufactured by Toray. Dow Corning (Stock); Momentive. High performance ．Materials.Japan) TSF400 (trade name), etc., but not limited to these examples.

When the total solid content of the composition for forming a hard coat layer is 100% by mass, it preferably contains 0.01% to 0.5% by mass of a silicone-based surfactant, more preferably 0.01% to 0.3% by mass %.

(Extinction particles)

In the hard coat layer or hard coat layer forming composition, it may contain matting particles with an average particle size of 1.0 μm to 15.0 μm, preferably 1.5 μm to 10.0 μm, for the purpose of imparting internal scattering properties or imparting surface irregularities. . In addition, in order to adjust the viscosity of the coating liquid, a polymer compound, an inorganic layered compound, or the like may also 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 applied on the base film and heated and dried. The drying method will be described later.

The coating method of the composition on the support includes: dip coating method, air knife coating method, curtain coating method, roll coating method, wire bar coating method, gravure coating method, micro gravure coating Method, die coating method, etc. Among them, the micro-gravure coating method, the wire bar coating method, and the die coating method are preferred, and the die coating method is more preferred. The details of the die coating method are described in detail in, for example, the specification of U.S. Patent No. 2681294 and Japanese Patent Laid-Open No. 2006-122889, and these descriptions can be referred to.

After the composition for forming a hard-coat layer is coated on the base film, drying is performed to remove the solvent contained in the composition, and the composition for forming a hard-coat layer is hardened to form a hard-coat layer. For example, drying can be performed by conveying the base film on which the composition layer for hard-coat layer formation was formed, and passing it through a heated area.

The temperature in the drying zone used for drying is preferably 25°C to 140°C. The temperature in the drying area may not necessarily be uniform. Preferably, the first half of the drying area is at a relatively low temperature, for example, in the range of 25°C to 100°C, and the latter half is at a relatively high temperature, for example, 60°C to 140°C. Range.

Among them, the temperature in the drying zone is preferably below the temperature at which components other than the solvent contained in the composition layer for forming the hard coat layer and the layer other than the composition layer for forming the hard coat layer formed on the support volatilize . More specifically, for example, a commercially available photo-radical generator used in combination with an ultraviolet curable resin has a compound that volatilizes about 10% of its amount in a warm wind at 120°C in a few minutes. In addition, Monofunctional acrylate monomers, bifunctional acrylate monomers, and the like have compounds that volatilize in warm air at 100°C. When these compounds that are easily volatilized at a heating temperature of about 100°C are used in the composition for forming a hard coat layer, the heating zone The temperature is preferably higher than the volatilization temperature of the solvent and lower than the temperature at which components other than the solvent start to volatilize.

When the composition for forming a hard coat layer is applied to the base film and then drying air is blown to the composition layer for forming a hard coat layer, in order to prevent drying of the composition layer for forming a hard coat layer. It is preferable that when the solid content concentration of the composition for forming a hard coat layer is 1% by mass to 50% by mass, the wind speed on the surface of the coating film of the composition for forming a hard coat layer is 0.1 m/sec to 2 m/sec. Within range.

In addition, as another preferable example of the drying conditions, the following method can be cited: after the composition for forming a hard coat layer is applied to the base film, the dry area and the base film are coated with the composition. The temperature difference between the temperature of the conveying roller and the temperature of the base film that the opposite surface is in contact with is adjusted to within 0°C to 20°C. By setting the temperature difference between the transport roller and the base film within the above range, it is possible to prevent uneven drying of the hard coat layer caused by uneven heat transfer on the transport roller, which is preferable.

In the drying area, after removing the solvent from the hard coat layer forming composition, the hard coat layer forming composition layer on the base film is passed through the hard coat layer hardened by ionizing radiation irradiation , Which can harden the hard coating.

When the composition for forming a hard coat layer is an ultraviolet curable composition, the hardened area is preferably an area irradiated with an ultraviolet lamp. The irradiation amount of the ultraviolet lamp is preferably in the range of 10 mJ/cm ² to 1000 mJ/cm ² . By irradiating ultraviolet rays with the above-mentioned irradiation amount, the hard coat layer can be cured suitably. When UV irradiation is performed, the radiation dose distribution in the width direction of the composition layer for forming a hard coat layer on the support conveyed in the hardened area is preferably relative to the maximum UV radiation dose at the center, including both ends. 50%~100% distribution, more preferably 80%~100% distribution.

In order to suppress the hardening hindrance caused by oxygen in the ultraviolet curable composition and further promote the surface hardening of the hard coat layer, the hardened area may be purged with an inert gas such as nitrogen to reduce the oxygen concentration. The oxygen concentration when reducing the oxygen concentration is preferably 0.01% to 5%, and the distribution of the oxygen concentration in the width direction in the hardened area is preferably 2% or less.

In order to promote the curing reaction of the ultraviolet curable composition, the temperature in the curing zone can be increased. From the viewpoint of accelerating the hardening reaction, it is preferable to set the temperature in the hardened region to 25°C to 100°C, more preferably 30°C to 80°C, and still more preferably 40°C to 70°C.

When forming the hard coat layer, other functional layers may be provided as needed. When forming a hard coat layer, when other functional layers are laminated in addition to the hard coat layer, a multi-layer coating in which a plurality of layers are simultaneously coated may be applied, or a successive coating formed in sequence may be carried out. The formation of the arbitrarily formed 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 easily bonding layer, a refractive index adjustment layer, and an ultraviolet absorbing layer.

[Decorative layer]

The decorative film of the present disclosure has a decorative layer. Regarding the decorative layer, at least a part of the decorative film has a decorative layer relative to the entire area in a plan view of the decorative film.

The decoration layer may be provided on the entire surface of the substrate, or may be provided on a part of it.

The decorative layer imparts various design properties to the decorative film.

As a decorative layer, for example, it can be used for image display when used as an image display panel. Characters or graphics that can be seen around the part, or a black border-shaped decorative layer provided in a frame shape on the image display part.

FIG. 3 is a plan view showing one aspect of the decorative film 10 of the present disclosure.

Among them, the decoration layer 14 of the decoration film 10 is as shown in FIG. That is, it is preferable to provide the following aspect as a black frame-shaped light-shielding layer on the back surface of a base material including a transparent polyester film, that is, on the side of the member where the decorative film is installed, to hide internal wiring, etc., and improve The appearance of a tablet terminal, etc.

The decoration layer may be formed as a resin layer containing a coloring agent corresponding to the purpose. The coloring agent contained in the decorative layer can be appropriately selected from various coloring agents according to the purpose of use. Generally, 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 on the entire surface of the decorative film as a background color, a white pigment is used.

As the black pigment contained in the decorative layer, for example, carbon black, titanium black, and the like can be cited. All of these have good light-shielding properties and are preferable when used as a light-shielding layer. As a white pigment, titanium oxide, zinc oxide, etc. are mentioned.

Regarding the decorative layer, a composition for forming a decorative layer containing a colorant and a binder resin may be applied to the surface of a substrate including a hard coat layer or a polyester film by a printing method to form a pattern, or may be formed by Set by transfer method. In addition, it can also be provided by forming a positive-type or negative-type decorative layer forming composition on the surface of a base material including a hard coat layer or a polyester film, and patterning it. Examples of the composition for forming a positive decorative layer include colorants, binder resins, photoacid generators, etc. to improve adhesion. The composition of the soluble compound of the agent resin. 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 the decorative layer, either a printing method or a transfer method may be used.

As a material for forming the decorative layer, for example, a printing ink containing a colorant that can be used on a resin substrate to form a colored film.

From a simple point of view, in the formation of the decorative layer, it is also a preferable aspect to use a printing ink containing the coloring agent described above and to form it by a printing method.

As a printing method, a screen printing method, a screen printing method, an inkjet printing method, a gravure printing method, a thermal transfer printing method, etc. are mentioned, for example. Among them, the screen printing method, the screen printing method, and the thermal transfer printing method are preferred from the viewpoint that a decorative layer with good hiding properties can be printed. With the printing method, a decorative layer can be easily provided in a pattern on the entire surface or a desired area.

As a printing ink used when forming a decorative layer by a screen printing method or a screen printing method, various inks used for printing on a film can be used, and a solvent system or a UV curing system can be used. In particular, the solvent-based ink only uses a drying oven to dry the solvent. Therefore, it does not require a UV irradiation device or the like, and can be printed at a low cost, so it can be suitably used.

As the ink used in the thermal transfer method, resin type or wax type can be used. Among them, the resin type can be suitably used because it is excellent in weather resistance.

In addition, the composition for forming a positive or negative decorative layer that can be patterned can also be applied to a substrate including a polyester film by a coating method, a transfer method, etc. A composition layer for forming a decoration layer is formed on at least one side of the surface, and a patterned decoration layer is formed by pattern exposure and development through exposure 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 already described, it is difficult to produce discoloration or printing defects, and it is easy to obtain suitable design.

The example of the preferable layer structure of the decorative film of this indication is shown below, but it is not limited to these layer structures. The following layer structures are described in order from the side of the member provided with the decorative film.

. Decorative layer/base material including polyester film/hard coat

. Substrate/hard coat/decorative layer including polyester film

. Substrate/decorative layer/hard coating including polyester film

Among them, from the viewpoint of design and scratch resistance, it is preferable that the decorative layer is arranged on one surface of the polyester film, and the hard coat layer is arranged on the surface of the polyester film on the opposite side to the surface on which the decorative layer is arranged. .

That is, it is preferable to have a decoration layer close to the member provided with the decoration film of this disclosure, and to have a polyester film as a base material, and a hard coat layer on the outermost surface in this order.

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

4A, FIG. 4B, and FIG. 4C are schematic side views showing a modified example of the laminate structure of a decorative layer/a base material including a polyester film/a hard coat layer. The decorative film shown in Figure 4A 10 has an aspect 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, from the bottom of FIG. 4A. The decorative film 20 shown in FIG. 4B has an aspect in which a base material 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 on which the decorative film 22 is arranged.

The decorative film of the present disclosure can have any of the above-mentioned laminated structures. The decorative film may have any layers other than the base material 16 including the polyester film, the hard coat layer 18, and the decorative layer 14 as necessary.

5A and 5B show a modification example of the schematic cross-sectional view on the line A-A of the decorative film 10 shown in FIG. 3.

The decorative film 22 shown in FIG. 5A shows the same laminated structure as the side view shown in FIG. 4C, and has a base material 16 including a polyester film on the side where the decorative film is arranged, and on the surface of the base material 16 including a polyester film The one-side peripheral edge portion of has a patterned decorative layer 14 having a shape as shown in FIG. 3 in a plan view, and a hard coat layer 18 is provided on the side of the base material 16 including a polyester film on the decorative layer 14 side.

In the decorative film 10 shown in FIG. 5B, one of the surfaces of the base material 16 including the polyester film has a peripheral edge portion of the surface on the member side where the decorative film 10 is arranged, as shown in FIG. 3 in a plan view. The decorative layer 14 in the shape of a pattern. The hard coat layer 18 is provided on the surface of the base material 16 including the polyester film on the opposite side to the surface having the decorative layer 14.

In addition, the layer structure of the decorative layer is not limited to the examples already described, 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, decorative layer, and hard coat layer. The optional layers include, for example, an easy-adhesive 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, a low refractive index layer and other refractive index adjustment layers, The antistatic layer, the ultraviolet absorbing layer, etc. are not limited to these layers. Regarding arbitrary layers, for example, the description of paragraph 0069 to paragraph 0091 of Japanese Patent No. 5048304 can be referred to.

(Low refractive index layer)

In the decorative film of the present disclosure, for the purpose of imparting a reflectance reduction effect, a low refractive index layer may be formed on the hard coat layer. The low refractive index layer is a layer having a refractive index lower than that of the hard coat layer. The thickness of the low refractive index layer in the case where the low refractive index layer is provided on the surface of the hard coat layer is preferably 50 nm to 200 nm, more preferably 70 nm to 150 nm, and still 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 directly 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, more preferably 70 nm to 100 nm.

The low refractive index layer is preferably obtained by curing the curable composition for forming the low refractive index layer.

As a preferred aspect of the curable composition for forming a low refractive index layer, there may be mentioned: (1) a fluorinated compound containing a crosslinkable functional group or a polymerizable functional group (2) The main component is the hydrolysis condensate of the fluorine-containing organosilane material, and (3) the monomer containing two or more ethylenically unsaturated groups and inorganic particles (especially preferably Inorganic particles having a hollow structure).

The low-refractive index layer-forming composition of (1) and (2) also preferably contains inorganic particles. As the inorganic particles, if an inorganic particle having a hollow structure with a lower refractive index than a solid inorganic particle is used, It is particularly preferable from the viewpoints of lowering the refractive index or adjusting the addition amount of inorganic particles and the refractive index.

(1) A composition containing a fluorine-containing compound having a crosslinkable or polymerizable functional group

Examples of the fluorine-containing compound having a crosslinkable or polymerizable functional group include a fluorine-containing polymer which is a copolymer of a fluorine-containing monomer and a monomer having a crosslinkable or polymerizable functional group. 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.

In addition, when the fluorine-containing polymer is used for the formation of a low refractive index layer, it may be appropriately combined with a curing agent having a polymerizable unsaturated group as described in Japanese Patent Laid-Open No. 2000-17028. And use. In addition, it is also preferable to use a fluorine-containing polymer and a fluorine-containing compound having a polyfunctional polymerizable unsaturated group in combination as described in Japanese Patent Laid-Open No. 2002-145952. As an example of the compound which has a polyfunctional polymerizable unsaturated group, the monomer which has 2 or more ethylenically unsaturated groups demonstrated as a curable resin of a low refractive index layer mentioned above is mentioned. In addition, make The compound used to form the low refractive index layer is also preferably the hydrolysis condensate of organosilane described in Japanese Patent Laid-Open No. 2004-170901, and particularly preferably an organosilane containing a (meth)acryloyl group The hydrolysis condensate. In particular, when a compound having a polymerizable unsaturated group in the polymer body is used, the combined use of these compounds has a greater effect than improving the scratch resistance and is better.

In the case where the polymer alone does not have sufficient curability, the composition for forming a low refractive index layer can be imparted with necessary curability by blending a cross-linking compound.

For example, when a hydroxyl group is contained in the polymer body, it is preferable to use various amine-based compounds as the hardener. The amino compound that can be used as a crosslinkable compound includes, for example, a compound containing two or more hydroxyalkylamino groups and alkoxyalkylamino groups in total, or both. Specific examples of the amine-based compound used as the crosslinkable compound include melamine-based compounds, urea-based compounds, benzoguanamine-based compounds, and acetylene carbamide-based compounds. In the hardening of these compounds, it is preferable to use an organic acid or a salt thereof.

(2) A composition that uses the hydrolysis condensate of a fluorine-containing organosilane material as the main component

A composition containing a hydrolysis condensate of a fluorine-containing organosilane compound as a main component has a low refractive index and a high hardness of the coating film surface, which is also preferable. The fluorine-containing organosilane material is preferably a condensate of a compound containing a hydrolyzable silanol at one or both ends with respect to a fluorinated alkyl group and a tetraalkoxysilane. The specific composition is 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

Furthermore, as another preferable aspect of the low refractive index layer, a low refractive index layer containing low refractive index particles and resin can be cited. 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 silica-based particles described in JP 2002-79616 A and the like.

The refractive index of the particles used in the low refractive index layer is preferably 1.15 to 1.40, more preferably 1.20 to 1.30.

Examples of the resin used in the low refractive index layer include resins derived from monomers having two or more ethylenically unsaturated groups.

In the composition for forming the 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 the low refractive index layer contains a radically polymerizable compound, relative to 100 parts by mass of the radically polymerizable compound, 1 part by mass to 10 parts by mass, preferably 1 part by mass to 5 parts by mass Parts of polymerization initiator.

Inorganic particles can be used in combination in the low refractive index layer. By using inorganic particles together, it is possible to impart scratch resistance to the low refractive index layer. In order to impart scratch resistance to the low refractive index layer, inorganic particles with 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 .

In the low refractive index layer, for the purpose of imparting antifouling, water resistance, chemical resistance, and smoothness, etc., well-known polysiloxane-based antifouling agents, Fluorine-based antifouling agent, smoothing agent, etc.

As an additive with a polysiloxane structure, polysiloxane containing reactive groups is added {e.g. 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 name), the above are manufactured by Shin-Etsu Chemical Industry (Stock); AK-5, AK- 30. AK-32 (trade name), the above are manufactured by Toagosei (Stock); "Silaplane FM0725", "Silaplane FM0721" (trade name), the above are JNC (shares) ) Manufacturing etc.} are also preferred. In addition, the silicone-based compounds described in Table 2 and Table 3 of JP 2003-112383 A can also be preferably used.

As the fluorine-based compound, a compound having a fluoroalkyl group is preferred. The carbon number of the fluoroalkyl group is preferably 1-20, more preferably 1-10, and may be linear (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 a branched structure (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.), or 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 contributes to bond formation or compatibility with the low refractive index layer coating. The fluorine-based compound preferably has a plurality of such substituents. In the case where the fluorine-based compound has a plurality of the substituents, the substituents may be The same can be different. Preferred examples of the substituent include: acryloyl, methacryloyl, vinyl, allyl, cinnamyl, epoxy, oxetanyl, hydroxyl, and polyoxyethylene Group, carboxyl group, amine group, etc.

The molecular weight of the fluorine-based compound is not particularly limited. The fluorine-based compound may be a polymer having a partial structure containing no fluorine atom, or may be an oligomer.

The content of fluorine atoms in the fluorine-based compound is not particularly limited, but is preferably 20% by mass or more, particularly preferably 30% to 70% by mass, and most preferably 40% to 70% by mass.

As an example of a preferable fluorine-based compound, R-2020, M-2020, R-3833, M-3833, and Optool DAC (above are Trade name), Megafac (registered trademark) F-171, F-172, F-179A, Defensa MCF-300, MCF-323 manufactured by DIC (the above are products) Name), etc., but not limited to these examples.

These polysiloxane fluorine compounds or compounds having a polysiloxane structure are preferably added in the range of 0.1% to 10% by mass of the total solid content of the low refractive index layer, particularly preferably 1% to 5% by mass. In the case of mass%.

[Use of decorative film]

The use of the decorative film of the present disclosure is not particularly limited, and if it is a use that requires scratch resistance and has design requirements, it can be suitably used without particular restrictions. Particularly in applications that require press processing for mounting on components, such as image display devices, touch panels, etc., peeling, cracks, and chipping of the decorative layer during processing are suppressed, so the effect is remarkable .

[Method of manufacturing decorative film]

The manufacturing method of the decorative film of the present disclosure includes: a step of forming a polyester film; a step of forming a decorative layer, forming a decorative layer on at least a part of one side of the polyester film; A hard coat layer is formed on one surface, and the polyester film forming step includes a lateral stretching step using a tenter type stretching device equipped with a plurality of clamps that move along a pair of rails respectively provided on both sides of the film conveying path , In a state where the unstretched polyester film is clamped by a clamp, it is stretched in a direction orthogonal to the film conveying path; the heat-fixing step is to heat the polyester film after the lateral stretch Fixing; and a heat relaxation step, heating the polyester film after the heat fixing step, and reducing the length of the film transport direction of the polyester film and the direction perpendicular to the film transport direction, and in the heat relaxation step The ratio of the reduction in the length of the polyester film in the direction orthogonal to the film conveying direction after the heat fixing step, that is, the relaxation rate in the direction orthogonal to the film conveying direction is set to 0.1% to 7%, and Set the relaxation rate of the heat-fixed polyester film in the film conveying direction to 0.1% to 7% to form the film conveying direction and the direction orthogonal to the film conveying direction at a temperature of 150°C for 30 minutes The heat shrinkage rate during the thermal history is all polyester films of 3.0% or less.

The polyester film forming step is as described in detail in the column of the polyester film, and the preferred aspects are also the same.

In the manufacturing method of the decorative film, first, a polyester film as a base material is formed. The order 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 coat layer forming step and the decorative layer forming step can be carried out first, and in addition, In the case where the hard coat layer and the decorative layer are formed on both sides of the substrate including the polyester film, the hard coat layer and the decorative layer may be simultaneously formed by a multi-layer coating or simultaneous transfer method.

[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 liquid crystal display devices (Liquid Crystal Display (LCD)), plasma display panels, electroluminescence displays, and cathode tube display devices.

Examples of liquid crystal display devices include twisted nematic (TN) type, super-twisted nematic (STN) type, triple super twisted nematic (TSTN) type, and 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 that includes a liquid crystal cell and the polarizing plate of the present disclosure disposed on at least one surface of the liquid crystal cell, and the decorative film of the present disclosure is disposed 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, it is also preferable that the image display element is 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 arranged on the top surface noodle.

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, a surface type electrostatic capacitance type touch panel, a projection type electrostatic capacitance type touch panel, a resistive film type touch panel, etc. are mentioned. The details will be described later as the resistive film type touch panel of the present disclosure and the electrostatic capacitance type touch panel of the present disclosure.

Furthermore, the so-called touch panel includes so-called touch sensors and touch pads. 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 bridge or a through-hole method , Or any of the single-area layer methods. In addition, with regard to the projection type electrostatic capacitive touch panel, alternating current (AC) driving is better than direct current (DC) driving, and it is more preferable to be a driving method that takes less time to apply voltage to the electrode.

(Resistive film type touch panel)

The resistive film type touch panel of the present disclosure is a resistive film type touch panel including the decorative film of the present disclosure.

The resistive film type touch panel includes a basic configuration in which the conductive films of a pair of upper and lower substrates having a conductive film are arranged in opposing positions with spacers interposed therebetween. Furthermore, the structure of the resistive film type touch panel is well-known, and the well-known technology can be applied without any limitation in the present disclosure.

(Electrostatic capacitive touch panel)

The electrostatic capacitive touch panel of the present disclosure is an electrostatic capacitor including the decorative film of the present disclosure. Capacitive touch panel.

As the method of the capacitive touch panel, a surface type capacitive type, a projection type capacitive type, and the like can be cited. The projection type electrostatic capacitance type touch panel includes a basic structure in which an X-axis electrode (hereinafter, also referred to as X electrode) and a Y-axis electrode (hereinafter, also referred to as Y electrode) orthogonal to the X electrode are arranged in an insulator. constitute. As a specific aspect, an aspect in which X electrodes and Y electrodes are formed on different surfaces on a single substrate, an aspect in which X electrodes, an insulator layer, and a Y electrode are sequentially formed on one substrate, and an aspect in which An aspect in which 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 above-mentioned basic structure). Furthermore, the structure of the capacitive touch panel is well-known, and the well-known technology can be applied without any limitation in the present disclosure.

[Example]

Examples and comparative examples are listed below to more specifically describe the decorative film and the like of the present disclosure. As long as they do not deviate from the gist of the present invention, the materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed. 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 quality standards.

[Example 1]

<Synthesis of raw material polyester>

(Raw material polyester 1)

As shown below, the direct esterification method is used and the continuous polymerization device is used to obtain The raw material polyester 1 (Sb catalyst-based PET) is obtained. The direct esterification method involves directly reacting terephthalic acid and ethylene glycol, then distilling off water, esterifying, and performing polycondensation under reduced pressure.

(1) Esterification reaction

4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol were mixed to form a slurry over 90 minutes, and the slurry was continuously supplied to the first esterification reaction tank at a flow rate of 3800 kg/h. Furthermore, the ethylene glycol solution of antimony trioxide was continuously supplied, and the reaction was carried out with stirring at 250° C. in the reaction tank and an average residence time of about 4.3 hours. During the reaction, antimony trioxide was continuously added in such an amount that the Sb addition amount became 150 ppm in terms of element conversion value.

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

(2) Polycondensation reaction

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

Furthermore, it is transferred to the second polycondensation reaction tank, in the second polycondensation reaction tank, under stirring, the temperature in the reaction tank is 276°C, the pressure in the reaction tank is 5torr (6.67×10 ^-4 MPa), and the residence time The reaction (polycondensation) proceeds in approximately 1.2 hours.

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

Next, the obtained reactant was sprayed into cold water in a strand shape, and cutting was immediately performed to produce polyester pellets "cross section: long diameter: about 4 mm, short diameter: about 2 mm, length: about 3 mm."

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

<Production of polyester film>

-Film forming steps-

After drying the raw material polyester 1 to a moisture content of 20 ppm or less, it was put into the hopper 1 of the uniaxial kneading extruder 1 having a diameter of 50 mm. The raw material polyester 1 was melted to 300°C, and extruded from a die through a gear pump and a filter (pore size: 20 μm) under the following extrusion conditions.

The extrusion conditions of the molten resin were that the pressure fluctuation was set to 1%, the temperature distribution of the molten resin was set to 2%, and the molten resin was extruded from the die. Specifically, 1% of the back pressure is applied to the average pressure in the barrel of the extruder, and heating is performed so that the piping temperature of the extruder becomes 2% higher than the average temperature in the barrel of the extruder .

The molten resin extruded from the die was extruded onto a cooling casting drum whose temperature was set to 25°C, and the cooling casting drum was brought into close contact with the cooling casting drum by an electrostatic application method. It peeled using the peeling roll arrange|positioned facing the cooling casting roll, and the unstretched polyester film 1 was obtained.

-Easy bonding layer formation-

The following compounds were mixed at the following ratio to prepare coating liquid H1 for forming an easily bonding layer.

(Coating liquid H1 for easy bonding layer formation)

The details of the compound used in the formation of the easy-adhesive layer are shown below.

-Polyester resin: (IC)-

Sulfonic acid water dispersion of polyester resin by copolymerization of monomers of the following composition

Monomer composition: (acid component) terephthalic acid/isophthalic acid/isophthalic acid-5-sodium sulfonate //(diol component) ethylene glycol/1,4-butanediol/diethylene two Alcohol=56/40/4//70/20/10 (mol%)

-Acrylic resin: (II)-

Aqueous dispersion of acrylic resin formed by polymerization of monomers of the following composition

Ethyl acrylate/n-butyl acrylate/methyl methacrylate/N-methylol acrylamide/acrylic acid=65/21/10/2/2 (mass%) emulsified polymer (emulsifier: anionic interface Active agent)

-Melamine compound: (VIB)-

Hexamethoxymethyl melamine

-Particles: (VII)-

Silicone with an average particle size of 150nm (the average particle size refers to the primary average particle size, that is, the average value of the primary particle size; it is described as the particle size in the following table).

-Easy bonding layer coating on both sides of polyester film-

By using the bar coating method using a wire rod, on one side of the unstretched polyester film 1, the coating liquid H1 for forming the easy-adhesive layer was adjusted so that the coating film thickness after stretching became 50nm, and the wire was used on the other side. Bar coating performs coating.

-Horizontal extension step-

The unstretched polyester film 1 was introduced into a tenter (transverse stretcher), and while the end of the film was clamped with a clamp, it was stretched laterally under the following method and conditions.

(Preheating section)

Heating was performed by hot air so that the surface temperature at the starting point of the extension became 89°C.

In addition, the surface temperature at the starting point of the extension is at the point where the extension starts, and the position of the center part in the width direction of the film is measured with a radiation thermometer (manufactured by Hayashi Electric Co., Ltd., model: RT61-2, used at an emissivity of 0.95). Measured.

(Extension)

While heating the preheated non-stretched polyester film 1 with hot air, it stretched laterally in the width direction (TD) under the following conditions using a tenter.

Furthermore, the surface temperature at each stretch magnification time point is at each stretch magnification time point Among them, it was obtained by measuring the position of the center part in the film width direction with a radiation thermometer (manufactured by Hayashi Electric Co., Ltd., model: RT61-2, used at an emissivity of 0.95).

<conditions>

. Transverse stretch magnification: 4.1 times

. Surface temperature at the point of 2 times extension time: 90℃

. Surface temperature at 3 times extension time point: 94℃

. Surface temperature at the end of extension: 95℃

(Heat fixing step)

Then, the nozzle was blown out from the hot air, and hot air from the vertical direction with respect to the film was blown onto the film, while controlling the surface temperature of the polyester film to the following range, heat fixing was performed.

<conditions>

. Maximum reach surface temperature (heat fixed temperature): 168℃

(Heat mitigation step)

In the heat relaxation step, use the method shown in Table 1 or Table 2 below to perform relaxation using the tenter extension device, and to adjust the conveying speed and the clamp interval during conveying, as shown in the following table 1 or The relaxation rate shown in Table 2.

The transfer tension in the heat relaxation step, the surface temperature of the polyester film during the heat relaxation (described in Table 1 and Table 2 as the "relaxed film surface temperature"), and the treatment time during heat relaxation (in Table 1 and Table 2) The cooling rate when the film surface temperature is in the range of 70°C ± 20°C during cooling after heat relaxation (described as "Relaxed cooling rate" in Table 1 and Table 2) is shown in Table 1 respectively. Or in Table 2.

(Cooling part)

Next, by blowing out the nozzle from the cold air, the cold air from the up-down direction with respect to the film is blown to the film, and it cools. The film was cooled so that the surface temperature when the film was released from the clamp of the tenter became 40°C.

In addition, the film surface temperature was obtained by measuring the position of the center part in the film width direction with a radiation thermometer (manufactured by Hayashi Electric Co., Ltd., model: RT61-2, used at an emissivity of 0.95).

(Recycling of membranes)

After cooling and releasing the film from the clamp, both ends of the polyester film were trimmed 20 cm each. The film width after trimming is 2m. Thereafter, after extrusion processing (knurling) on both ends with a width of 10 mm, a film with a length of 10,000 m was wound into a roll form with a tension of 18 kg/m.

The polyester film 1 used for the production of the decorative film of Example 1 wound in a roll form with a thickness of 150 μm was produced as described above.

[Film measurement result]

The following physical properties of the obtained polyester film 1 were measured. 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 polyester film 1, a contact-type film thickness meter (manufactured by Anritsu) was used, and 50 locations were sampled at equal intervals across 0.5 m in the longitudinally extending direction (length direction), and then the film width Direction (direction orthogonal to the length direction) After sampling 50 points across the entire width of the film at equal intervals (50 equally divided in the width direction), the thickness of the 100 points was measured. The average thickness of the above-mentioned 100 points was calculated and used as the thickness of the polyester film.

<Re, Rth, Re/Rth ratio>

The Re and Rth of the obtained film were determined by the aforementioned method. Calculate the Re/Rth ratio based on the obtained Re and Rth.

<Heat shrinkage>

Regarding the polyester film, a sample piece M of the polyester film was obtained by cutting into a width of 30 mm and a length of 120 mm in the MD direction and the TD direction, respectively, and cut two reference lines in the longitudinal direction so as to become 100 mm apart.

After placing 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. Set the measured interval after heat treatment as A[mm], and use the value calculated by the formula "100×(100-A)/100" based on the interval 100mm before the treatment and the interval A mm after the treatment. [%] is 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 9 locations in total was used as the measurement value. The results are shown in Table 1 or Table 2.

[Formation of Hard Coat]

A composition 1 for forming a hard coat layer having the following composition was prepared.

(Composition of composition 1 for forming hard coat layer)

The coating liquid for forming a hard coat layer is applied by the following method.

The uniaxially stretched polyester film used in Example 1 wound into a roll form was unrolled, and as a subsequent step, the coating liquid for forming a hard coat layer as described above was applied by the following method.

For the hard coat layer, the easy-adhesive layer is provided on one side of the film, and the easy-adhesive layer is formed on the side where the easy-adhesive layer is formed by the die coating method using a slit die 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 zone at a temperature of 60° C. for 150 seconds. After that, it is transported to the hardening area to harden the hard-coat layer forming composition. In the hardened area, make the oxygen concentration about 0.1% under nitrogen purge, use 160W/cm ² air-cooled metal halide lamp (manufactured by Eyegraphics (Co., Ltd.), irradiation illuminance 400mW/cm ² , irradiation The hard coat layer was hardened by applying 500 mJ/cm ² of ultraviolet rays, and the laminate on which the hard coat layer was formed was wound up.

In addition, in other Examples and Comparative Examples, the base films described in Table 1 and Table 2 were also used to form a hard coat layer in the same manner. When the easy-adhesive layer is not provided, a hard coat layer is formed on any one side of the film as the base material.

<Film Thickness of Hard Coat>

The thickness of the hard coat layer was calculated by measuring the thickness of the produced hard coat layer with a contact-type film thickness meter, and subtracting the thickness of the polyester film measured in the same manner from it. The results are shown in Table 1 or Table 2.

[Formation of decorative layer]

(1. Manufacture of transfer film for forming decorative layer)

<Preparation of composition for forming decorative layer>

The composition 1 (coloring composition) for forming a decorative layer was obtained in the following order.

(Composition of composition 1 for forming a decorative layer)

[化15]

(K pigment dispersion 1)

[化16]

First, weigh the K pigment dispersion 1 in the amount described in the composition of the composition 1 for forming the decorative layer, mix at a temperature of 24°C (±2°C), and perform 150 revolutions per minute (Round Per Minutes, RPM). ) Stir for 10 minutes to obtain solution 1. Next, weigh methyl ethyl ketone, 1-methoxy-2-propyl acetate, binder, 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 above, and stirred at 150 RPM for 30 minutes at a temperature of 24° C. (± 2° C.).

<Production of transfer film>

On a temporary support for a polyethylene terephthalate film having a thickness of 75 μm, a coating liquid for a thermoplastic resin layer containing the following formulation H1 was applied and dried using a slit-shaped nozzle. Next, a coating liquid for an intermediate layer containing the following formula P1 was applied and dried. After that, the aforementioned composition 1 for forming a decorative layer is applied and dried. In the manner described above, a thermoplastic resin layer with a dry film thickness of 15.1 μm, an intermediate layer with a dry film thickness of 1.6 μm, and a composition layer for forming a black decorative layer with a dry film thickness of 2.0 μm are provided on the temporary support. Finally, press Protective film (polypropylene with a thickness of 12μm) membrane). In this way, a transfer film was produced in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the composition layer for forming a black (K) decorative layer, and the protective film were integrated.

(Coating liquid for thermoplastic resin layer: Formulation H1)

(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 with weight average molecular weight of 30,000, 30% by mass solution of methyl ethyl ketone, manufactured by DIC, trade name: Megafac F780F)

(Coating liquid for intermediate layer: formula P1)

(2. Formation of decorative layer using transfer and patterning)

<Transfer>

Remove the protective film from the obtained transfer film on the surface of the polyester film 1 with the easy-adhesive layer on the side where the hard coat layer is not formed, and remove the exposed surface of the black decorative layer forming composition layer The direction in contact with the surface of the polyester film 1 is overlapped, and a laminator (manufactured by Hitachi Industrial Co., Ltd. (Lamic II type)) is used. The rubber roller temperature is 130°C, the linear pressure is 100N/cm, and the conveying The lamination is carried out at a speed of 2.2m/min. Then, the temporary support body of polyethylene terephthalate was peeled at the interface with the thermoplastic resin layer, and the temporary support body was removed.

<Patternization of decorative layer>

After peeling off the temporary support, use a proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high-pressure mercury lamp to make the substrate and the mask (with only use Set the distance between the exposure mask surface and the black decorative layer forming composition layer to 200μm in the state where the quartz exposure mask of the image pattern remaining on the periphery of the polyester film stands upright, and the exposure 70mJ/cm ² for pattern exposure.

Next, the triethanolamine-based developer (containing 30% by mass of triethanolamine, with pure The product name: T-PD2 (manufactured by Fuji Film Co., Ltd.) is diluted with water 12 times (mixed with 1 part of T-PD2 and 11 parts of pure water) at 30°C with a flat nozzle pressure Perform spray development at 0.1 MPa for 20 seconds to remove the thermoplastic resin layer and the intermediate layer. Next, after blowing air to the upper surface of the polyester film 1 for liquid discharge, pure water is sprayed for 10 seconds to perform pure water spray cleaning, and air is blown to reduce liquid accumulation on the substrate.

After that, use sodium carbonate/sodium bicarbonate-based developer (trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) with pure water to dilute to 5 times (at the ratio of 1 part of T-CD1 to 4 parts of pure water) Mixed) liquid), the composition layer for forming a decorative layer was developed for 30 seconds at a shower pressure of 0.1 MPa at 30°C, and washed with pure water.

Next, use a cleaning solution containing a surfactant (a liquid obtained by diluting the trade name: T-SD3 (manufactured by Fujifilm Co., Ltd.) to 10 times with pure water) at 33°C with a cone-shaped nozzle pressure of 0.1 MPa was blown by spray for 20 seconds to clean the composition layer for forming a decorative layer. Furthermore, ultrapure water was sprayed at a pressure of 9.8 MPa using an ultra-high pressure cleaning nozzle to remove residues.

In this manner, 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 side on which 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 out with a length of 50 mm and a width of 50 mm to prepare a decorative film as a test sample. Put it in a heating furnace at a temperature of 150°C for 30 minutes. After that, take out the decorative film and cool it to room temperature. Place it on a flat place, and measure the distance between the surface of the flat part and the measurement target part of the decorative film. The distance, that is, the amount of warpage of the decorative film is taken as the curl value (H). The measurement target parts are the four corners of the square test piece and the center of one side of the square, which is a total of eight places. The curl value was set as the average value of the curl values measured in the eight measurement target parts described above, and the average value of the curl values measured on the five test pieces was calculated as the curl value shown in Table 1 or Table 2. value.

When the decorative film sheet is curled into a convex shape with respect to a flat place after heating, the decorative film sheet is turned over and arranged in a concave shape to measure the curl value. The results are shown in Table 1 or Table 2 below.

<Pressing Evaluation>

The decorative film was subjected to 10 press processing, and the chipping of the hard coat layer on the pressed end surface, the peeling state of the decorative layer and the base material, and the peeling state of the base material and the hard coat layer were evaluated based on the following criteria.

A: No chipping/flaking at all

B: 1 chipping/flaking occurred

C: Fracture/flaking occurred 2 times

D: Fracture/flaking occurred more than 3 times

<Surface Scratch Resistance Evaluation>

Measure the surface of the decorative film according to the method described in JIS K-5600 5-4 (with Hard coat side) pencil hardness. If the pencil hardness is H or higher, it is evaluated as having practically sufficient surface scratch resistance.

A: The pencil hardness is more than 5H

B: Pencil hardness is 3H~4H

C: Pencil hardness is H~2H

D: Pencil hardness is less than H

<Visibility Evaluation>

Between the polarizing plates installed in the crossed Nicols, the hard coat layer was sandwiched so that the alignment angle of the hard coat layer was inclined at 45° with respect to the absorption axis of the polarizing plate, and the LED backlight was irradiated from the rear, and evaluated based on the following criteria Visibility.

A: No rainbow-like unevenness is seen at all

B: Almost no rainbow-like unevenness is seen

C: Rainbow-like unevenness is slightly seen, but it is tolerable

D: Obviously see rainbow-like unevenness

[Example 2~Example 16, Comparative Example 1~Comparative Example 6]

In Example 1, the thickness of the polyester film used in the base material, the conditions of the stretching step, the presence or absence of an easy-to-bond layer, the presence or absence of a hard coat layer, and the hard coat layer were changed as described in Table 1 or Table 2 below, respectively. Except for the composition, the decorative film of each example and comparative example was produced in the same manner as in Example 1. In addition, 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 The resin substrate shown.

The details of the base film used in Example 16, Comparative Example 1 to Comparative Example 4 are as follows.

-Biaxial extension PET-

In the polyester film used in Example 1, a biaxially stretched polyester film stretched in the MD direction at a stretching ratio of 3.2 times in addition to the stretching in the TD direction was obtained as a base film.

-PC-

Polycarbonate (PC) film: Sumika Acrylic Sales (Stock), Technolloy C1000 (trade name), thickness 150μm

-PMMA-

Polymethyl methacrylate (PMMA) film: Sumika acrylic acid sales (shares), Technolloy S1000 (trade name), thickness 150μm

-PMMA/PC/PMMA-

A film laminated in the order of PMMA/PC/PMMA, Sumika Acrylic Sales (Stock), Technolloy C-101 (trade name), thickness 300μm

The formulations of the hard coat layer forming composition 2 used in Example 15 to Example 17 are as follows.

(Composition of composition 2 for forming hard coat layer: used in Example 15)

(Composition of composition 3 for forming hard coat layer: used in Example 16 to Example 17)

According to the evaluation results described in Table 1 and Table 2, compared with the decorative film of the comparative example, the decorative film of the example whose curl value after a thermal history at 150° C. for 30 minutes is 5 mm or less and the thermal shrinkage rate (150°C, 30 minutes) polyester film of 3.0% or less is used as the base material. The decorative film of the examples has good scratch resistance, and the occurrence of cracks, chipping and peeling between layers during press processing are all obtained inhibition.

Among them, by using a uniaxially stretched polyester film as a base material, in addition to the effects of the present invention, the visibility of the decorative film is further improved.

Claims (20)

A decorative film, which has a polyester film, a decorative layer and a hard coat, is produced when a film with a length of 50 mm and a width of 50 mm is applied to the decorative film at a temperature of 150° C. and a thermal history of 30 minutes The curl value is 5mm or less. The decorative film according to the first item of the scope of patent application, wherein the decorative layer is provided in at least a part of the entire area of the decorative film in a plan view. The decorative film as described in item 1 or item 2 of the scope of patent application, wherein the in-plane retardation Re of the polyester film at a measurement wavelength of 589 nm is in the range of 3000 nm to 50000 nm. A decorative film, which has a polyester film, a decorative layer and a hard coat. When a thermal history of 150°C for 30 minutes is applied to the polyester film, one direction in the surface of the polyester film and the one The heat shrinkage rate in the direction orthogonal to the plane is 3.0% or less, and the thermal shrinkage is generated when the decorative film has a length of 50 mm and a width of 50 mm and a thermal history of 150°C for 30 minutes. The curl value of the decorative film is 5 mm or less. The decorative film according to item 4 of the scope of patent application, wherein the polyester film is a uniaxially aligned polyester film. The decorative film according to item 4 or item 5 of the scope of the patent application, wherein the decorative layer is disposed on one side of the polyester film, and the hard coat layer is disposed on the polyester film and is disposed with The surface of the decorative layer is the surface on the opposite side. The decorative film according to item 4 or item 5 of the scope of patent application, wherein at least a part of the decorative film has the decorative layer with respect to 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 scope of patent application, wherein the in-plane retardation Re of the polyester film at a measurement wavelength of 589 nm is in the range of 3000 nm to 50000 nm. The decorative film according to item 4 or item 5 of the scope of patent application, wherein the in-plane retardation Re of the polyester film at a measurement wavelength of 589nm is relative to the thickness direction retardation of the polyester film at a measurement wavelength of 589nm The ratio of Rth is in the range of 0.6 to 1.2. The decorative film described in item 4 or item 5 of the scope of patent application has an easy-adhesive 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 coat layer is H or higher. The decorative film according to item 4 or item 5 of the scope of patent application, wherein the thickness of the hard coat layer is 5 μm or more. The decorative film according to item 4 or item 5 of the scope of patent application, wherein 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), and relative to the total solid content of the hard coat layer, containing 15% by mass to 70% by mass The structure derived from the following a), the structure derived from the following b) from 25% by mass to 80% by mass, the following c) from 0.1% by mass to 10% by mass, and the following c) from 0.1% to 10% by mass d); a) A compound having an alicyclic epoxy group and a group containing an ethylenically unsaturated double bond in the molecule, and a molecular weight of 300 or less b) having three or more compounds containing an ethylenically unsaturated double bond in the molecule Bond-based compound c) a radical polymerization initiator d) a cationic polymerization initiator. An image display device comprising an image display element and the decorative film according to any one of items 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 in the scope of patent application, and the decorative film is provided on the outermost surface. A method for manufacturing a decorative film, comprising: a step of forming a polyester film; a step of forming a decorative layer, forming a decorative layer on at least a part of one side of the polyester film; and a step of forming a hard coat layer, forming a step on the polyester film A hard coat layer is formed on at least one side of the film, and the decorative film has a curl value of 5 mm or less when a thermal history of 150° C. and 30 minutes is applied to a film with a length of 50 mm and a width of 50 mm. The polyester film forming step includes a lateral stretching step, using a tenter type stretching device equipped with a plurality of clamps that move along a pair of rails provided on both sides of a film conveying road, and clamped by the clamps In the state of the unstretched polyester film, extend in a direction orthogonal to the film conveying path; the heat fixing step is to perform heat fixation by heating the horizontally stretched polyester film; And a heat relaxation step, heating the polyester film after the heat fixing step, and reducing the length of the polyester film in the film conveying direction and the direction perpendicular to the film conveying direction, and relaxing in the heat In the 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 the direction orthogonal to the film transport direction is set to 0.1% ~7%, to form a polyester film with a heat shrinkage rate of 3.0% or less in the film conveying direction and the direction orthogonal to the film conveying direction at a temperature of 150°C and a heat history of 30 minutes. The method of manufacturing a decorative film according to claim 17, wherein the reduction of the length of the polyester film in the direction perpendicular to the film conveying direction in the heat relaxation step includes reducing the length of the film conveying The distance between a pair of rails on both sides of the road, and reducing the length of the polyester film in the film transport direction in the heat relaxation step includes reducing the distance between the plurality of moving jigs. The method of manufacturing a decorative film as described in item 17 or item 18 of the scope of the patent application, wherein the length of the film conveying direction of the polyester film is reduced in the heat relaxation step The degree includes applying tension in the film conveying direction of the polyester film and reducing the length while conveying under heating conditions. The manufacturing method of the decorative film as described in item 17 or item 18 of the scope of patent application, wherein the conveying tension of the polyester film in the heat relaxation step is 10N/m width ~ 80N/m width, and the heating of the polyester film The film surface temperature is 110°C~190°C, and the heat treatment time is 10 seconds to 600 seconds. When cooling 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.

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