JP6563110B2 - Decorative film, image display device, touch panel and method for producing decorative film - Google Patents

Description

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

Image display devices such as cathode ray tube display devices, plasma displays, electroluminescence displays, fluorescent display devices, field emission displays, and liquid crystal display devices (LCDs), or smartphones and tablet terminals equipped with touch panels Various displays of small terminals may provide a hard coat layer and a laminated film having a decorative layer on a support containing a resin as a main component.
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 provided for the purpose of applying various designs such as concealing the wiring arranged in the apparatus main body on the image display surface.
Especially for small terminals equipped with a touch panel, the image display surface has good wear resistance for the purpose of effectively preventing the film from being scratched because the screen is directly touched with a finger or touched with a touch pen. It is required to be.

  When the strength of the hard coat layer is improved to make it a hard film, the decorative film with the hard coat layer and the decorative layer is processed and fixed on the display. Adjustments are made. The polyester film base material, hard hard coat layer, and decorative layers containing decorative colorants that have different physical properties from the hard coat layer have different mechanical strength, stretchability, etc., so delamination during punching Or cracks may occur in the hard hard coat layer.

For example, as a hard coat film for an image display surface that has an appropriate surface hardness and can be used in combination with a decorative layer, a hard coat film having an acrylic resin base material and specific physical property values has been proposed ( For example, refer to JP2014-109712A).
Moreover, it has a decorative layer on the surface of a resin base material such as a polycarbonate base material and a polyethylene terephthalate base material, and a region where the decorative layer is not provided is filled with a hard coat layer, and can be manufactured at low cost. And the cover film for image display surfaces which can be made into a thin layer is proposed (for example, refer to JP, 2014-35493, A).
A surface coating material for a casing, in which the resin layer contains particles and has a specific haze value and Martens hardness, has been proposed and described to give a good feel to the surface (for example, JP2013-244624A). See the official gazette).

However, according to the study by the present inventors, it was found that the decorative film having a resin base material, a decorative layer, and a hard coat layer has greatly different physical properties of each component, and thus various problems occur. .
For example, in the film described in Japanese Patent Application Laid-Open No. 2014-109712, when the surface hardness of the hard coat layer is increased, only the hard coat layer becomes hard, and the adhesion between the adjacent decorative layer and the resin base material decreases. Sometimes. Furthermore, due to the physical properties when subjected to thermal history, when the decorative film is punched into an appropriate shape, delamination between the hard coat layer and the resin substrate or the decorative layer occurs, or punching Cracks or cracks may occur during processing. In JP-A-2014-109712, as a comparative example, an embodiment in which a polyethylene terephthalate base material is used instead of an acrylic resin base material is disclosed, but rainbow unevenness and incident light are displayed during image display. It is described that blackout occurs due to phase difference. That is, a hard coat film using a polyethylene terephthalate base material is considered to have a problem in optical properties, and in the technique described in JP 2014-109712 A, it is assumed that a polyester film is used as the base material. Not.

  Moreover, since the area | region which does not have a decoration layer is filled with the hard-coat layer, the adhesiveness of a hard-coat layer and a decoration layer improves the cover film of Unexamined-Japanese-Patent No. 2014-35493. However, the cover film described in Japanese Patent Application Laid-Open No. 2014-35493 has received a thermal history between the resin base material and the hard coat layer in the same manner as the film described in Japanese Patent Application Laid-Open No. 2014-109712. Due to the physical properties of the case, delamination between the hard coat layer and the resin substrate may occur, or cracks or cracks may occur during the punching process.

  Since the casing covering material described in JP2013-244624A assumes premise of in-line coating when covering the surface of the casing, punching processing for adjusting the size when mounting on the casing It is not supposed to do. Since the coating material described in JP2013-244624A has a resin layer containing particles, the touch when touched with fingers is softened. However, as described above, it is not assumed that punching or the like is performed, and even if punching is performed, the resin layer includes particles, so the suitability for punching is low, and cracking occurs when punching is performed. Concerned.

An object of an embodiment of the present invention is to provide a decorative film, an image display device including the decorative film, and a touch panel, in which generation of cracks and cracks during punching processing is suppressed and excellent in scratch resistance. It is in.
Moreover, the subject of another embodiment of this invention provides the manufacturing method of the decorating film which can manufacture the decorating film which generation | occurrence | production of the crack at the time of a punching process was suppressed, and was excellent in abrasion resistance. There is.

The present disclosure includes the following embodiments.
<1> A decorative film having a polyester film, a decorative layer, and a hard coat layer, and a thermal history of 30 ° C. and a temperature of 150 ° C. is given to a film piece having a length of 50 mm and a width of 50 mm. A decorative film having a curl value of 5 mm or less.

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

<4> It is a decorative film having a polyester film, a decorative layer, and a hard coat layer. When the polyester film is given a thermal history of 150 ° C. for 30 minutes, one direction in the plane of the polyester film; A decorative film having a thermal shrinkage rate of 3.0% or less in one direction and a direction orthogonal in the plane.
<5> The decorative film according to <4>, wherein the polyester film is a uniaxially oriented polyester film.

<6> The decorative layer is disposed on one surface of the polyester film, and the hard coat layer is disposed on the surface opposite to the surface on which the decorative layer of the polyester film is disposed <4> or < The decorative film according to 5>.
The decoration film as described in any one of <4>-<6> which has a decoration layer in at least one part with respect to the whole area | region in the planar view of a <7> decoration film.
<8> The decorative film according to any one of <4> to <7>, wherein the polyester film has a thickness of 40 μm to 500 μm.

<9> The decorative film according to any one of <4> to <8>, wherein the in-plane retardation Re at a measurement wavelength of 589 nm of the polyester film is in the range of 3000 nm to 50000 nm.
<10> The ratio of the in-plane retardation Re at the measurement wavelength 589 nm of the polyester film to the retardation Rth in the thickness direction at the measurement wavelength 589 nm of the polyester film is in the range of 0.6 to 1.2 <4> to < The decorative film according to any one of 9>.
<11> The decorative film according to any one of <4> to <10>, which has an easy-adhesion 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 more.
<13> The decorative film according to any one of <4> to <12>, wherein the thickness of the hard coat layer is 5 μm or more.
<14> The hard coat layer includes at least a structure derived from the following a), a structure derived from the following b), the following c) and the following d), and has a structure derived from the following a) with respect to the total solid content of the hard coat layer. 15 to 70% by mass, 25% to 80% by mass of the structure derived from b) below, 0.1% to 10% by mass of the following c), 0.1% to 10% by mass of the following d) < The decorative film according to any one of 4> to <13>.
a) a compound having one alicyclic epoxy group and one group containing an ethylenically unsaturated double bond in the molecule and having a molecular weight of 300 or less; b) three or more ethylenic groups in the molecule. Compound having group containing saturated double bond c) radical polymerization initiator d) cationic polymerization initiator

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

<17> Using a tenter-type stretching device including a plurality of clips respectively traveling along a pair of rails installed on both sides of the film transport path, the unstretched polyester film is gripped with the clips in the film transport path. A transverse stretching step that stretches in a direction orthogonal to the heat treatment, a heat setting step that heat-sets the polyester film after transverse stretching, heats the polyester film after the heat-setting step, and transports the polyester film. And a thermal relaxation step of narrowing the length in the direction orthogonal to the direction of the film and the film conveyance direction, and in the thermal relaxation step, the relaxation rate in the film conveyance direction of the polyester film after the heat setting step is 0.1% to 7 % And the rate of relaxation in the direction perpendicular to the film transport direction is 0.1% to 7%, Polyester film forming step of forming a polyester film having a thermal shrinkage rate of 3.0% or less when a thermal history at a temperature of 150 ° C. for 30 minutes in a direction orthogonal to the direction and the film conveying direction is given, polyester A decoration layer forming step of forming a decorative layer on at least a part of one surface of the film and a hard coat layer forming step of forming a hard coat layer on at least one surface of the polyester film A method for producing a film.

<18> Narrowing the length in the direction orthogonal to the film transport direction of the polyester film in the thermal relaxation step includes narrowing the distance between the pair of rails installed on both sides of the film transport path. The method for producing a decorative film according to <17>, wherein reducing the length of the polyester film in the film conveying direction includes narrowing a plurality of clip intervals.
<19> Shrinking the length of the polyester film in the film relaxation direction in the thermal relaxation step includes applying a tension to the film transport direction of the polyester film and shrinking the length while transporting under heating conditions <17 > Or <18> The method for producing a decorative film according to <18>.

<20> In the thermal relaxation step, the transport tension of the polyester film is 10 N / m to 80 N / m, the film surface temperature during heating of the polyester film is 110 to 190 ° C., and the heat treatment time is 10 Seconds to 600 seconds, and during cooling after narrowing the length of the polyester film, the cooling rate when the film surface temperature of the polyester film is in the range of 70 ° C. ± 20 ° C. is 100 ° C./min to 2000 ° C./min. The manufacturing method of the decorating film as described in any one of <17>-<19>.

According to an embodiment of the present invention, it is possible to provide a decorative film, an image display device including a decorative film, and a touch panel that are suppressed in cracking during punching and have excellent scratch resistance.
Moreover, according to another embodiment of the present invention, there is provided a method for producing a decorative film capable of producing a decorative film in which the occurrence of cracks during punching is suppressed and which has excellent scratch resistance. be able to.

It is the schematic which shows the detail of the curl value measuring method of a decorating film, and is a top view of the decorating film piece for curl value measurement. It is the schematic which shows the detail of the curl value measuring method of a decorating film, and is a schematic side view which shows the state of the decorating film piece in curl value measurement. It is the schematic which shows the detail of the curl value measuring method of a decoration film, and is a schematic side view which shows the state of the curled decoration film which needs inversion. It is a partial schematic diagram showing an example of the configuration of a tenter stretching apparatus used in the transverse stretching step. It is a top view which shows one Embodiment of a decorating film. It is a schematic side view which shows an example of the modification of the layer structure of a decorating film. It is a schematic side view which shows an example of the modification of the layer structure of a decorating film. It is a schematic side view which shows an example of the modification of the layer structure of a decorating film. It is a schematic sectional drawing which shows an example of the modification of the layer structure of a decorating film. It is a schematic sectional drawing which shows an example of the modification of the layer structure of a decorating film.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments or specific examples, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. Moreover, when the unit is attached | subjected to one of the numerical value described before and behind "-", it means that it is the same unit in the whole numerical range.
In this specification, “(meth) acryloyl group” refers to one or both of “acryloyl group” and “methacryloyl group”, and “(meth) acrylate” refers to any of “acrylate” and “methacrylate”. Or “(meth) acryl” refers to one or both of “acryl” and “methacryl”.
In this specification, unless otherwise specified, room temperature means 25 ° C.

[Decorative film]
The decorative film according to the first embodiment of the present invention is a decorative film having a polyester film, a decorative layer, and a hard coat layer. The curl value of the decorative film generated when a heat history of 150 ° C. for 30 minutes is given is 5 mm or less.
“Give a thermal history of 150 ° C. for 30 minutes” means that the decorative film is left to stand for 30 minutes in a 150 ° C. temperature atmosphere and heated.

A method for measuring the curl value of the decorative film will be described with reference to FIG.
First, a decorative film is cut into a length of 50 mm and a width of 50 mm, and a decorative film as a test sample piece is prepared as a film piece having a length of 50 mm and a width of 50 mm (hereinafter sometimes referred to as a decorative film piece) 10. To do. FIG. 1A is a plan view showing a cut decorative film piece 10. In the plan view of the decorative film piece 10, the measurement target portion of the curl value is schematically indicated by ●. The measurement target locations are 8 points in total including 4 corner portions of the cut decorative film piece 10 and 4 central portions of each square piece.
The obtained decorative film piece 10 shown in FIG. 1A is placed in a heating furnace having a temperature of 150 ° C. for 30 minutes.
Then, after adjusting the humidity for 8 hours in an environment of a temperature of 25 ° C. and a humidity of 60%, as shown in FIG. 1B, the decorative film piece 10 is allowed to stand in a flat place 12, and the surface of the flat place 12 is defined as a measurement reference plane. To do. The distance between the reference plane and the measurement target location on the decorative film piece 10 (indicated by an arrow H in FIG. 1B), that is, the measurement target location and the reference plane in the perpendicular line dropped from the measurement target location on the decorative film piece 10 to the reference plane And measure the distance to the curl value. FIG. 1B is a side view showing a state in which the decorative film piece 10 is placed in a flat place 12, and the distance indicated by an arrow H in FIG. 1B is a curl value.
When the decorative film piece 10 is curled in a convex shape with respect to the flat place 12 as shown in FIG. 1C after heating, the decorative film piece 10 is inverted and recessed, that is, the state shown in FIG. 1B And make measurements.
The curl value of the decorative film 10 to be measured is the average value of the curl values measured at the eight measurement target portions of the decorative film piece described above.

In the decorative film of this embodiment, the curl of the decorative film piece 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.
When the curl measured at the above-described upper limit of the decorative film exceeds 5 mm, when the decorative film is punched and applied, the polyester film and the decorative layer are easily peeled off, which is not preferable.

  The decorative film according to the second embodiment of the present invention is a decorative film having a polyester film, a decorative layer, and a hard coat layer, and gave a thermal history of 150 ° C. for 30 minutes to the polyester film. At this time, the heat shrinkage rate in one direction in the plane of the polyester film and the direction orthogonal to the one direction in the plane are both 3.0% or less.

  Hereinafter, an example of an embodiment in the present disclosure is referred to as a decorative film of the first embodiment, an example of another embodiment is referred to as a decorative film of the second embodiment, and the decorative film of each embodiment. Each component of the will be sequentially described. In this specification, when referring to both the first embodiment and the second embodiment, they may be collectively referred to as “embodiments in the present disclosure”.

[Polyester film]
The decorative film which concerns on 1st Embodiment and 2nd Embodiment has a polyester film as a base material.
In the heat history described above, the decorative film of the present disclosure includes a polyester film having a low thermal shrinkage rate as a substrate as one of means for achieving a curl condition of 5 mm or less.
As a polyester film having a small heat shrinkage rate, when a polyester film as used in the decorative film of the second embodiment described above is given a heat history of 150 ° C. for 30 minutes, the polyester film has an in-plane surface. Examples thereof include a polyester film having a thermal shrinkage rate of 3.0% or less in one direction and a direction orthogonal to the one direction in the plane.
Other means include increasing the thickness of the polyester film as the base material, stretching the polyester film at a high magnification, and increasing the elastic modulus of the film used for the base material. Is also effective.

As a polyester film used for the decorative film of the first embodiment, when a polyester film is given a thermal history of 150 ° C. and 30 minutes, one direction in the plane of the polyester film, and the one direction and the in-plane It is preferred that the polyester film has a thermal shrinkage rate of 3.0% or less in the direction perpendicular to each other.
When the decorative film of the second embodiment gives the polyester film a thermal history at a temperature of 150 ° C. for 30 minutes, the heat in one direction in the plane of the polyester film and in the direction orthogonal to the one direction in the plane. The base material is a polyester film having a shrinkage rate of 3.0% or less.

<Characteristics of polyester film>
(Heat shrinkage)
The polyester film that can be used for the decorative film of the present disclosure is one direction in the plane, for example, a film conveyance direction (hereinafter referred to as “MD direction”) and a direction orthogonal to the one direction ( For example, when one direction is “MD direction”, the heat when the following heat history is given in both directions (Transverse Direction, hereinafter referred to as “TD direction”) orthogonal to the film transport direction is given. The shrinkage rate is preferably 3.0% or less, and the decorative film of the second embodiment is orthogonal to the one direction in the plane when the following thermal history is given, and orthogonal to the one direction. The base material is a polyester film having a thermal shrinkage rate of 3.0% or less.
The heat history when measuring the thermal shrinkage of the polyester film is to stand at a temperature of 150 ° C. for 30 minutes.
Hereinafter, the uniaxially stretched polyester film which is a preferable aspect of the base material in the decorative film of the present disclosure will be described as an example.
The polyester film preferably has a heat shrinkage rate of 3.0% or less after a heat history of 150 ° C. for 30 minutes in any one direction of the film and a direction orthogonal to the one direction, 1.5% The following is more preferable, and 0.5% or less is more preferable.
By using a polyester film having a heat shrinkage rate of 3.0% or less measured under the conditions described above, the thermal stability of the polyester film as a base material is further improved, and the generation of wrinkles during the production of a decorative film, It is possible to more effectively suppress delamination and cracking when punching a decorative film.

The polyester film has an absolute value of 0.6% or less of the difference between the thermal shrinkage rate in one direction in the plane of the polyester film and the thermal shrinkage rate in the direction orthogonal to the one direction in the plane under the conditions described above. Is preferably 0.4% or less, and more preferably 0.3% or less.
The difference in thermal shrinkage between the two directions perpendicular to each other in the plane of the polyester film makes the properties of the polyester film even more uniform. When making a decorative film by laminating other layers on the polyester film, punching Generation of wrinkles of the decorative film at the time of processing or when fixing the punched decorative film to a member can be more effectively suppressed.

In this specification, as the heat history, the heat shrinkage rate under the condition of 30 minutes at a temperature of 150 ° C., that is, the heat shrinkage rate of the film after being heated at 150 ° C. for 30 minutes is hereinafter referred to as “heat shrinkage rate (150 Sometimes referred to as “° C. for 30 minutes”.
A method for measuring the thermal shrinkage will be described.
Two reference lines are preliminarily placed at a position that is 100 mm apart in the length direction on a sample piece M of a polyester film cut in a direction 30 mm wide and 120 mm long in one direction. After the sample piece M is left in a heating oven at 150 ° C. for 30 minutes under no tension, the sample piece M is cooled to room temperature, and the interval between the two reference lines is measured. The interval after processing to be measured is A [mm]. The numerical value [%] calculated by using the formula “100 × (100−A) / 100” from the interval 100 mm before the treatment and the interval Amm after the treatment is used as the thermal contraction rate (150 ° C. of the sample piece M). 30 minutes).
In each direction, the measurement is performed at three locations for each of three sample pieces in each direction, and the arithmetic average of the measurement results of a total of nine points is used as the measurement value.
For example, when one direction is the MD direction, the heat shrinkage in the MD direction is also referred to as MD heat shrinkage, and the ratio is referred to as the MD heat shrinkage rate. Therefore, the thermal contraction rate in the direction orthogonal to the film width direction during the production of the polyester film becomes the contraction rate in the film transport direction and can be referred to as MD thermal contraction rate.

In this specification, the heat shrinkage rate (150 ° C. for 30 minutes) in the direction orthogonal to the above-described one direction after standing at 150 ° C. for 30 minutes is defined as follows.
When measuring the heat shrinkage rate in a direction orthogonal to the above-mentioned one direction, a polyester resin film cut to a width of 30 mm and a length of 120 mm in the direction orthogonal to the above-described one direction is used as a sample piece M. In advance, two reference lines are placed at positions that are 100 mm apart in the length direction. The sample piece M is allowed to stand for 30 minutes in a heating oven at 150 ° C. under no tension, and then the sample piece M is cooled to room temperature, and the interval between the two reference lines is measured. The interval after processing to be measured is A [mm]. A numerical value [%] calculated by using the formula “100 × (100−A) / 100” from the interval 100 mm before processing and the interval Amm after processing is orthogonal to one direction of the sample piece 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 contraction can be referred to as TD thermal contraction, and the ratio thereof can be referred to as the TD thermal contraction rate.

The polyester film having a heat shrinkage ratio (150 ° C., 30 minutes) of 3.0% or less is preferably a uniaxially oriented polyester film.
An unstretched polyester film formed by melt film formation or solution film formation is subjected to lateral stretching, heat setting, and heat relaxation by the method described later, whereby a polyester film having the aforementioned preferable heat shrinkage rate can be easily obtained.

(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.
Since the thickness of the polyester film is within the above range, the decorative film has sufficient rigidity and can be suitably used as an alternative material for glass. Is suppressed. Moreover, the dimensional stability of a decoration film becomes more favorable because the thickness of a polyester film exists in the said range.
The thickness of the polyester film can be measured using, for example, a contact-type film thickness meter.
In the measurement, 50 points are sampled in each direction of the polyester film and in a direction perpendicular to the one direction, and the average thickness of the measured values of the thickness at these points is obtained to obtain the thickness of the polyester film.

-Re (Retardation in the film plane)-
The polyester film used for the decorative film of the present disclosure preferably has an in-plane retardation Re of 4000 nm to 50000 nm at a measurement wavelength of 589 nm. Hereinafter, the in-plane retardation Re in this specification refers to a value at a measurement wavelength of 589 nm unless otherwise specified.
If Re of the polyester film is 3000 nm or more, rainbow unevenness is difficult to be visually recognized, and if it is 50000 nm or less, the required film thickness does not become too thick, and it is suppressed that the rigidity is too strong, and handling becomes easy.
From this viewpoint, Re of the polyester film is more preferably 5000 nm to 40000 nm, and further preferably 7000 nm to 33000 nm.

-Re / Rth-
The polyester film preferably has a ratio (Re / Rth) of the retardation Re in the film plane at the measurement wavelength of 589 nm to the retardation Rth in the film thickness direction at the measurement wavelength of 589 nm (Re / Rth). .
If the Re / Rth of the polyester film is 0.6 or more, rainbow unevenness is hardly visible, and if it is 1.2 or less, the film is difficult to become brittle. Hereinafter, the retardation Rth in the film thickness direction in the present specification indicates a value at a measurement wavelength of 589 nm unless otherwise specified.
From this viewpoint, Re / Rth of the polyester film is more preferably 0.7 to 1.15, and still more preferably 0.8 to 1.1.

The retardation Rth in the thickness direction of the polyester film is preferably 3000 nm to 80000 nm, more preferably 4000 nm to 60000 nm, and still more preferably 6000 nm to 40000 nm.
If the Rth of the polyester film is 3000 nm or more, it is easy to make a film. It is preferable.

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

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

In addition, Nz value of a polyester film is represented by following formula (3).
Formula (3): Nz = (nx−nz) / (nx−ny)

In this specification, Re, Rth, and Nz at a wavelength λnm can be measured as follows.
Using two polarizing plates, the orientation axis direction of the polyester film is determined, and this is defined as one direction in the plane. A 4 cm × 2 cm rectangle is cut out at a position where the orientation axis directions are perpendicular to each other and used as a measurement sample. About the obtained measurement sample, the biaxial refractive index (nx, ny) perpendicular to each other and the refractive index (nz) in the thickness direction were measured by an Abbe refractometer (manufactured by Atago Co., Ltd., NAR-4T, measurement wavelength 589 nm). The absolute value (| nx−ny |) of the biaxial refractive index difference was determined as the anisotropy (Δnxy) of the refractive index. The thickness y ₁ (nm) of the polyester film was measured using an electric micrometer (manufactured by Fine Reef, Millitron 1245D), and the unit was converted to nm. Measured nx, ny, nz, Re from the value of _{y 1,} Rth, Nz was calculated.

Re and Rth at the above measurement wavelength of 589 nm are adjusted by the type of polyester resin used in the film, the amount of the polyester resin and additives, the addition of the retardation developer, the film thickness, the film stretching direction and the stretching ratio, etc. can do.
There is no particular limitation on the method for controlling Re and Re / Rth of the polyester film within the ranges. Examples of a method for controlling Re and Re / Rth of the polyester film include a stretching method.

(Constituent material, layer structure, and surface treatment of polyester film)
The polyester film used for the decorative film of the present disclosure includes a polyester resin. The content ratio of the polyester resin in the entire polyester film is usually 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more.
The polyester film may be a single-layer film having a polyester resin as a main component or a multilayer film having at least one layer having a polyester resin as a main component.
Moreover, the polyester film may be surface-treated on both surfaces or one surface of the film. The surface treatment may be surface modification by corona treatment, saponification treatment, heat treatment, ultraviolet irradiation, electron beam irradiation, or the like, or may be thin film formation by coating or vapor deposition of a polymer compound, metal or the like.

The polyester film may have an easy adhesion layer on at least one surface.
The thickness of the easy adhesion 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.
When the thickness of the easy-adhesion layer is 30 nm or more, the cushion effect by the easy-adhesion layer is easily obtained, and the shear plane normal stress and the shear plane yield stress are suppressed from excessively increasing. Moreover, if the thickness of an easily bonding layer is 300 nm or less, the cushion effect of an easily bonding layer is not too strong, and it is suppressed that a shear plane normal stress and a shear plane yield stress fall too much.

More preferably, the easy-adhesion layer contains particles, and the height at which the particles protrude from the surface of the easy-adhesion layer is equal to or greater than the film thickness of the easy-adhesion layer.
The height at which the particles protrude from the surface of the easy adhesion layer is an average value at 5 points in the 1 mm square easy adhesion layer.
When the particle protruding from the surface of the easy-adhesive layer is less than the film thickness of the easy-adhesive layer (preferably, the coating layer), the slipperiness decreases and wrinkles are likely to occur. .
The type of particles that can be included in the easy-adhesion layer is not particularly limited, and specific examples include, for example, silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, and oxidation. Examples of the particles include titanium and zirconium oxide, and silica, aluminum oxide, titanium oxide, and zirconium oxide are preferable. Further, the heat-resistant organic particles described in JP-B-59-5216, JP-A-59-217755 and the like may be used. Examples of other heat-resistant organic particles include particles such as thermosetting urea resin, thermosetting phenol resin, thermosetting epoxy resin, and benzoguanamine resin.
The particle diameter is preferably such that the height at which the particles protrude from the surface of the easy adhesion layer is equal to or greater than the film thickness of the easy adhesion layer. It is preferable to use particles adjusted with the primary average particle diameter, but as a result, the particles may be aggregated so that the height at which the particles protrude from the surface of the easy-adhesion layer is equal to or greater than the film thickness of the easy-adhesion layer. . In the case of agglomerated particles, the height at which the particles protrude from the surface of the easy adhesion layer can be confirmed by measuring the secondary average particle diameter.

(1-1) Polyester resin As the polyester resin contained in the polyester film, for example, a polyester resin having a composition of [0042] of WO2012 / 157762 is preferably used.
As specific polyester resins, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycyclohexanedimethylene terephthalate (PCT), etc. can be used. More preferably, PET is more preferable. PEN tends to have a small Re / Rth.
As the polyester resin, polyethylene terephthalate is most preferable. 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 a structural unit derived from terephthalic acid as a dicarboxylic acid component and a structural unit derived from ethylene glycol as a diol component, and 80 mol% or more of all repeating units are preferably ethylene terephthalate. The structural unit derived from other copolymerization components may be included. Other copolymer components include isophthalic acid, p-β-oxyethoxybenzoic acid, 4,4′-dicarboxydiphenyl, 4,4′-dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, adipic acid Dicarboxylic acid components such as sebacic acid, 5-sodium sulfoisophthalic acid, 1,4-dicarboxycyclohexane, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, ethylene oxide adduct of bisphenol A, polyethylene glycol, Examples of the diol component include polypropylene glycol and polytetramethylene glycol. These dicarboxylic acid components and diol components can be used in combination of two or more if necessary. It is also possible to use the carboxylic acid component or diol component in combination with an oxycarboxylic acid such as p-oxybenzoic acid. As another copolymer component, a dicarboxylic acid component and / or a diol component containing a small amount of an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like may be used.
The production method of polyethylene terephthalate includes terephthalic acid and ethylene glycol, so-called direct polymerization method in which other dicarboxylic acids and / or other diols are directly reacted as necessary, dimethyl ester of terephthalic acid and ethylene glycol, if necessary Any production method such as a so-called transesterification method in which a dimethyl ester of another dicarboxylic acid and / or another diol is transesterified can be applied.

(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. Hereinafter, it is more preferably 0.54 or more and 0.7 or less. In order to make IV into the above-mentioned range, when synthesizing a polyester resin, in addition to the melt polymerization described later, solid phase polymerization may be used in combination.

(1-2-2) Acetaldehyde content The polyester resin preferably has an acetaldehyde content of 50 ppm or less. More preferably, it is 40 ppm or less, Most preferably, it is 30 ppm or less. Acetaldehyde easily causes a condensation reaction between acetaldehyde, water is generated as a side reaction product, and the hydrolysis of the polyester may proceed with the generated water. The lower limit of the acetaldehyde content is practically about 1 ppm. In order to keep the acetaldehyde content within the above range, the oxygen concentration in each step such as melt polymerization and solid phase polymerization during resin production is kept low, the oxygen concentration during resin storage and drying is kept low, film Adopting methods such as lowering the heat history applied to the resin with an extruder, melt piping, die, etc. at the time of production, adjusting to conditions that do not cause strong shear locally by the screw configuration of the extruder when melting, etc. I can do it.

(1-3) Catalyst For the polymerization of the polyester resin, Sb, Ge, Ti, and / or Al-based catalyst is used, preferably Sb, Ti, and / or Al-based catalyst, more preferably Al-based catalyst. .
That is, it is preferable that the polyester resin used as the raw material resin for the polyester film is a resin polymerized using an aluminum catalyst.
By using an Al-based catalyst, Re is more likely to be expressed than when other catalysts (for example, Sb or Ti) are used, and PET can be thinned. In other words, the use of an Al-based catalyst means that the orientation is easier. This is presumed to be due to the following reasons.
The Al-based catalyst has a lower reactivity (polymerization activity) than the Sb-based catalyst or Ti-based catalyst, and thus the reaction is mild, and a by-product (diethylene glycol unit: DEG) is hardly generated.
As a result, the regularity of PET increases, and it is easy to align and to express Re.

(1-3-1) Al-based catalyst As the Al-based catalyst, the Al-based catalyst described in [0013] to [0148] of WO2011 / 040161 ([0021] to [0123] of US2012 / 0183761). The contents described in these publications are incorporated herein by reference.
Although there is no restriction | limiting in particular as a method of manufacturing a polyester resin by superposition | polymerization using an Al type catalyst, Specifically, [0091]-[0094] of WO2012 / 008488 ([0144] of US2013 / 0112271) To [0153]), the contents described in these publications are incorporated herein.
Further, Al-based catalysts include, for example, [0052] to [0054], [0099] to [0104] of JP2012-122051 ([0045] to [0047], [0091] of WO2012 / 029725. [0096]), the contents of which are described in these publications are incorporated herein.
The amount of the Al-based catalyst is preferably 3 ppm to 80 ppm, more preferably 5 ppm to 60 ppm, and still more preferably 5 ppm to 40 ppm as the amount of Al element with respect to the mass of the polyester resin.

(1-3-2) Sb-based catalyst As the Sb-based catalyst, Sb-based catalysts described in JP-A-2012-41519, [0050] and [0052] to [0054] can be used.
Although there is no restriction | limiting in particular as a method of superposing | polymerizing a polyester resin using a Sb type | system | group catalyst, Specifically, it can superpose | polymerize according to [0086]-[0087] of WO2012 / 157762.

(1-4) Additive It is also preferable to add a known additive to the polyester film. Examples of known additives include UV absorbers, particles, lubricants, anti-blocking agents, thermal stabilizers, antioxidants, antistatic agents, light resistance agents, impact modifiers, lubricants, dyes, pigments, etc. Can be mentioned. However, since the polyester film generally requires transparency, it is preferable to keep the additive amount to a minimum.

(1-4-1) Ultraviolet (UV) absorber The polyester film may contain an ultraviolet absorber in order to prevent the liquid crystal or the like of the liquid crystal display from being deteriorated by ultraviolet rays. The ultraviolet absorber is a compound having ultraviolet absorbing ability, and is not particularly limited as long as it is an ultraviolet absorber that can withstand the heat applied in the production process of the polyester film.
Examples of the ultraviolet absorber include an organic ultraviolet absorber and an inorganic ultraviolet absorber, and an organic ultraviolet absorber is preferable from the viewpoint of transparency. The ultraviolet absorber described in [0057] of WO2012 / 157762 or the cyclic imino ester-based ultraviolet absorber described below can be used.

  Examples of the cyclic iminoester-based ultraviolet absorber include, but are not limited to, 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, 2 -Phenyl-3,1-benzoxazin-4-one, 2- (1- or 2-naphthyl) -3,1-benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazine -4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3, 1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one, 2-cyclo Xyl-3,1-benzoxazin-4-one, 2-p- (or m-) phthalimidophenyl-3,1-benzoxazin-4-one, N-phenyl-4- (3,1-benzoxazine- 4-On-2-yl) phthalimide, N-benzoyl-4- (3,1-benzoxazin-4-one-2-yl) aniline, N-benzoyl-N-methyl-4- (3,1-benzo Oxazin-4-one-2-yl) aniline, 2- (p- (N-methylcarbonyl) phenyl) -3,1-benzoxazin-4-one, 2,2′-bis (3,1-benzoxazine -4-one), 2,2′-ethylenebis (3,1-benzoxazin-4-one), 2,2′-tetramethylenebis (3,1-benzoxazin-4-one), 2,2 '-Decamethylenebis 3,1-benzoxazin-4-one, 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) [Note that 2,2′-p-phenylenebis (Also referred to as (3,1-benzoxazin-4-one)), 2,2′-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6- or 1,5-naphthylene) bis (3,1-benzoxazin-4-one), 2,2 ′ -(2-Methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 '-(2-nitro-p-phenylene) bis (3,1-benzoxazin-4-one) ), 2,2 ′-(2-chloro-p-phenylene) bis (3,1-ben Zooxazin-4-one), 2,2 ′-(1,4-cyclohexylene) bis (3,1-benzoxazin-4-one), 1,3,5-tri (3,1-benzoxazine-4) -On-2-yl) benzene, 1,3,5-tri (3,1-benzoxazin-4-on-2-yl) naphthalene, 2,4,6-tri (3,1-benzoxazine-4) -On-2-yl) naphthalene, 2,8-dimethyl-4H, 6H-benzo (1,2-d; 5,4-d ') bis (1,3) -oxazine-4,6-dione, , 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-benzoxazin-4-one), 6,6′-bis (2-phenyl-4H, 3 , 1-benzoxazin-4-one), 6,6′-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-methylenebis (2-phenyl-4H, 3 , 1-benzoxazin-4-one), 6,6′-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-ethylenebis (2-phenyl-4H) , 3,1-benzoxazin-4-one), 6,6′-butylenebi (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-butylenebis (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-benzoxazin-4-one), 6,6′-sulfonylbis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6 ′ -Carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-carbonylbis (2-phenyl-4H, 3,1-benzoxazin-4-one), 7, 7'-methylenebis (2-methyl- 4H, 3,1-benzoxazin-4-one), 7,7′-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 7,7′-bis (2-methyl-) 4H, 3,1-benzoxazin-4-one), 7,7′-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-oxybis (2-methyl) -4H, 3,1-benzoxazin-4-one), 7,7'-sulfonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-carbonylbis (2 -Methyl-4H, 3,1-benzoxazin-4-one), 6,7'-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7'-bis (2 -Phenyl-4H, 3,1-benzoxazin-4-one, 6 7'-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7'-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), etc. It is done.

  Among the above compounds, when considering the color tone, a benzoxazinone-based compound that is difficult to be yellowed is preferably used. For example, a compound represented by the following formula (4) is more preferably used.

Formula (4)

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

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

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

  The amount of the ultraviolet absorber that may be contained in the polyester film is usually 10.0% by mass or less, preferably 0.3% by mass to 3.0% by mass with respect to the entire film. When an ultraviolet absorber in an amount exceeding 10.0% by mass is contained, the ultraviolet absorber may bleed out on the surface, which may cause a decrease in surface functionality such as a decrease in adhesion.

Moreover, when a polyester film has a laminated structure, it is preferable that it is at least 3 layer structure, and it is preferable that the ultraviolet absorber is mix | blended with the intermediate | middle layer (layers other than outermost layer). By blending the UV absorber in the intermediate layer, the UV absorber can be prevented from bleeding out to the film surface, and as a result, the properties such as the adhesiveness of the film can be maintained.
For example, the master batch method described in [0050] to [0051] of WO2011 / 162198 can be used for blending the ultraviolet absorber.

(1-4-2) Other additives Other additives may be used for the polyester film, for example, the additives described in [0058] of WO2012 / 157762 can be used, and the contents described in this publication Is incorporated herein.

(Manufacture of polyester film)
The polyester film is preferably produced by the following production method.
Using a tenter-type stretching device that includes a plurality of clips that respectively run along a pair of rails installed on both sides of the film transport path, the unstretched polyester film is gripped by the clips and orthogonal to the film transport path A transverse stretching step of stretching in a direction to perform,
A heat setting step for heat setting by heating the polyester film after transverse stretching;
Including a heat relaxation step of heating the polyester film after the heat setting step and narrowing the length of the polyester film in the direction perpendicular to the film transport direction and the film transport direction,
In the thermal relaxation step, the relaxation rate in the direction orthogonal to the film conveyance direction, which is the ratio of narrowing the length in the direction orthogonal to the film conveyance direction of the polyester film after the heat setting step, is 0.1% to 7%. And by making the relaxation rate in the film transport direction of the heat-fixed polyester film 0.1% to 7%,
Suitable as a base for a decorative film having a thermal shrinkage rate of 3.0% or less when giving a heat history at a temperature of 150 ° C. for 30 minutes in the direction perpendicular to the film conveyance direction and the film conveyance direction. A polyester film can be produced.
Here, “unstretched polyester film” means a polyester film in which the refractive indexes of MD and TD are both 1.590 or less. Polyester films having a refractive index of 1.590 or less are included in the unstretched polyester film.
Hereinafter, as a preferred embodiment of the method for producing a polyester film, a case where an unstretched polyester film is formed by melt extrusion and then stretched in the transverse direction to produce a uniaxially oriented polyester film will be described.

<Melting and kneading>
The unstretched polyester film is preferably formed into a film by melt-extruding a polyester resin.
It is preferable to dry the polyester resin or the master batch of the polyester resin and additive produced by the above-described master batch method to a moisture content of 200 ppm or less, and then introduce the melt into a single or twin screw extruder and melt it. In order to suppress the decomposition of the polyester resin in the extruder, it is also preferred to melt in nitrogen or vacuum. The detailed conditions can be carried out according to these publications, for example, with the aid of [0051] to [0052] (US 2013/0100378 publication [0085] to [0086]) disclosed in Japanese Patent No. 4926661 The contents of which are incorporated herein by reference. Furthermore, it is also preferable to use a gear pump in order to increase the delivery accuracy of the molten resin (melt). It is also preferable to use a filter having a pore diameter of 3 to 20 μm for removing foreign substances.

<Extrusion or coextrusion>
Although it is preferable to extrude the melt containing the polyester resin melt-kneaded from the die, it may be extruded as a single layer or may be extruded as a multilayer (coextrusion). When extruding in multiple layers, for example, a layer containing an ultraviolet absorber (UV agent) and a layer not containing it may be laminated. This is preferable from the viewpoint of suppressing bleed out and suppressing deterioration of the polarizer due to the UV agent.
When the UV agent bleeds out, the UV agent on the film surface is transferred to the roll in contact with the film in the film manufacturing process, increasing the coefficient of friction between the film and the roll, and is not preferable because scratches are likely to occur. .
When the polyester film is produced by being extruded in multiple layers, the thickness (ratio to the total layer) of the preferred inner layer (layer other than the outermost layer) of the obtained polyester film is preferably 50% or more and 95% or less, more preferably 60%. It is 90% or less, more preferably 70% or more and 85% or less. Such lamination can be performed by using a feed block die or a multi-manifold die.

<Cast>
As a method for producing a polyester film, for example, according to the description of [0059] of JP-A-2009-269301, a melt extruded from a die is extruded onto a casting drum, cooled and solidified, and an unstretched polyester film (raw fabric) Is preferred.
In the method for producing a polyester film, the refractive index in the film transport direction (MD direction) of the unstretched polyester film is preferably 1.590 or less, more preferably 1.585 or less, and further preferably 1.580 or less.

When producing a polyester film, the crystallinity of the unstretched polyester film is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less. In addition, the crystallinity degree of an unstretched polyester film here means the crystallinity degree of the center part of a film width direction (TD direction).
When adjusting the degree of crystallinity, the temperature of the end of the casting drum may be lowered, or air may be blown onto the cast drum.
The crystallinity can be calculated from the density of the film. That is, the density X (g / ^cm 3) of the film density at a crystallinity of ^{0% Y = 1.335g / cm 3} , using density Z = 1.501g / cm ³ at 100% crystalline below The crystallinity (%) can be derived from the calculation formula.
Crystallinity = {Z × (XY)} / {X × (ZY)} × 100
The density is measured according to JIS K7112.

<Formation of an arbitrary polymer layer>
On the melt-extruded unstretched polyester film, an arbitrary polymer layer according to the purpose may be formed by coating before or after stretching described later.
As an arbitrary polymer layer, the functional layer which the polarizing plate may have generally can be mentioned, It is preferable to form an easily bonding layer especially. The easy-adhesion layer can be applied by the method described in [0062] to [0070] of WO2012 / 157762, for example.

<Preheating>
FIG. 2 schematically shows an example of the configuration of a tenter stretching apparatus used in the transverse stretching step.
As a preheating step until the start of stretching in the transverse stretching step, it is preferable to preheat an unstretched polyester film at a temperature increase rate of 600 ° C./min or less. If the heating rate of the film until the start of stretching in the transverse stretching process is 600 ° C./min or less, the film will be stretched in a state where the molecular chain has sufficiently moved, and the shear plane normal stress and shear plane yield stress will increase excessively. Is suppressed.
From this viewpoint, the temperature increase rate in the preheating step is more preferably 500 ° C./min or less, and further preferably 400 ° C./min or less.

<Horizontal stretching>
In the transverse stretching step, as shown in FIG. 2, a tenter type stretching device (also referred to as “tenter”) having a plurality of clips 13 running along a pair of rails installed on both sides of the film transport path is used. Transverse stretching is performed with both edges of the stretched polyester film held by the clips 13. In addition, you may hold | grip an unstretched polyester film with a clip from the stage of a preheating process.

  There is no particular limitation on the tenter stretching device having the clip 13 that travels along a pair of rails installed on both sides of the film conveyance path. A pair of endless rails is usually used as the pair of rails. In addition, a clip is synonymous with a holding member.

  An unstretched polyester film is stretched transversely. The lateral stretching is performed in a direction (TD) orthogonal to the film transport direction (MD) while transporting an unstretched polyester film along the film transport path. That is, the lateral stretching can be achieved by holding both ends of the film with clips and widening between the clips while heating.

  By stretching in the transverse direction, the retardation Re in the in-plane direction can be greatly expressed. 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 transverse stretching.

The surface temperature at the start of stretching in the transverse stretching step is preferably from 80 ° C to 95 ° C, more preferably from 82 ° C to 93 ° C, and still more preferably from 84 ° C to 92 ° C.
If the surface temperature at the start of stretching in the transverse stretching step is 80 ° C. or higher, the orientation and orientation crystallization do not proceed excessively in the stretching step, and the shear plane normal stress and shear plane yield stress are prevented from excessively increasing. Further, the rise in Rth is suppressed, and the Re / Rth ratio is 0.6 or more, so that the visibility of rainbow unevenness is suppressed.
If the surface temperature at the start of stretching in the transverse stretching process is 95 ° C. or less, the growth of spherulites due to insufficient orientation is suppressed, the shear surface normal stress and shear surface yield stress are excessively decreased, and the film is prevented from becoming cloudy. In addition, Re is likely to rise sufficiently.

In the method for producing a polyester film, the surface temperature at the end of stretching in the transverse 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 further preferably 93 ° C. or higher and 100 ° C. or lower.
When the surface temperature at the end of stretching in the transverse stretching step is 90 ° C. or higher, the orientation and orientation crystallization do not proceed excessively in the stretching step, and the shear plane normal stress and shear plane yield stress are prevented from excessively increasing. Further, the rise in Rth is suppressed, and the Re / Rth ratio is 0.6 or more, so that the visibility of rainbow unevenness is suppressed.
If the surface temperature at the end of stretching in the transverse stretching process is 105 ° C. or less, the growth of spherulites due to insufficient orientation is suppressed, the shear surface normal stress and shear surface yield stress are excessively decreased, and the film is prevented from becoming clouded. Therefore, Re that affects the suppression of rainbow unevenness is likely to rise sufficiently.

The surface temperature is gradually raised from the start of stretching in the transverse stretching step to the end of stretching. Here, “gradually rising” may be a continuous increase or a stepwise increase.
The difference in surface temperature between the end of stretching and the start of stretching is preferably 1 ° C. or higher, more preferably 3 ° C. or higher, and most preferably 5 ° C. or higher.
When the surface temperature is gradually increased from the start of stretching to the end of stretching, spherulites are less likely to be formed and the orientation is prevented from proceeding excessively. It becomes difficult to see.

The transverse draw ratio in the transverse drawing step is preferably controlled in the range of 3.3 times to 4.8 times, more preferably 3.5 times to 4.5 times, and more preferably 3.7 times to 4.3 times. Even less than double is more preferable.
When the transverse draw ratio is 3.3 times or more, the shear plane normal stress and the shear plane yield stress of the film are suppressed from excessively decreasing, and the reduction of Re effective in suppressing rainbow unevenness is suppressed. When the transverse draw ratio is 4.8 times or less, the shear plane normal stress and the shear plane yield stress of the film are prevented from being excessively increased and becoming brittle.

In the transverse stretching step, the surface temperature of the film in the range of 1 to 2 times the transverse stretching ratio is preferably 80 ° C. or more and 92 ° C. or less, more preferably 82 ° C. or more and 91 ° C. or less, and further 84 ° C. or more and 91 ° C. or less. preferable.
The film surface temperature in the range of 1 to 2 times or less in the transverse stretching step is 80 ° C. or higher, so that the orientation and orientation crystallization do not proceed excessively in the stretching stage, and the shear plane normal stress and shear plane An excessive increase in yield stress is suppressed. Further, the rise in Rth is suppressed, and the Re / Rth ratio is 0.6 or more, so that the visibility of rainbow unevenness is suppressed.
When the film surface temperature is in the range of 1 to 2 times or less in the transverse stretching step in the transverse stretching process, spherulite growth due to insufficient orientation is suppressed, and shear plane normal stress and shear plane yield stress are suppressed. Is reduced too much, and rainbow unevenness is not visually recognized without Re sufficiently increasing.

In the transverse stretching step, the surface temperature of the film in the transverse stretching ratio 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 further 87 ° C. or higher and 96 ° C. or lower. preferable.
In the transverse stretching step, when the surface temperature of the film in the transverse stretching ratio range of 2 to 3 times or less is 85 ° C. or more, the orientation and orientation crystallization do not proceed excessively in the stretching stage, and shear plane normal stress and shear plane yielding are achieved. It is suppressed that the stress rises too much. Further, the rise in Rth is suppressed, and the Re / Rth ratio is 0.6 or less, so that the visibility of rainbow unevenness is suppressed.
In the transverse stretching step, if the surface temperature of the film at a transverse stretching ratio of 2 to 3 times or less is 97 ° C. or less, the growth of spherulites due to insufficient orientation is suppressed, and shear plane normal stress and shear plane yield stress are suppressed. Is suppressed from falling too much. In addition, Re, which is effective in suppressing rainbow unevenness, is sufficiently increased, and rainbow unevenness is suppressed from being visually recognized.

In the transverse stretching step, the film surface temperature in the range where the transverse stretching ratio is 3 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 and 100 ° C. or lower.
In the transverse stretching process, if the surface temperature of the film in the range of 3 times or more in the transverse stretching ratio is 90 ° C. or more, the orientation and orientation crystallization do not proceed excessively in the stretching stage, and the shear plane normal stress and shear plane yield stress increase. Too much is suppressed. Further, the rise of Rth is suppressed, and the Re / Rth ratio is 0.6 or more, thereby preventing the rainbow unevenness from being visually recognized.
In the transverse stretching step, if the surface temperature of the film at a transverse stretching ratio of 3 times or more is 102 ° C. or less, the growth of spherulites due to insufficient orientation is suppressed, and the shear plane normal stress and shear plane yield stress are too low. It is suppressed. In addition, Re increases sufficiently, and the visibility of rainbow unevenness is suppressed.

  In addition, in order to gradually increase the surface temperature from the start of stretching to the end of stretching, in the transverse stretching step, the surface temperature of the film in the range of 1 to 2 times the transverse stretching ratio, the transverse stretching ratio is 2 to 3 times. The surface temperature of the film in the following range and the surface temperature of the film in the range where the transverse draw ratio is 3 times or more do not become lower than the surface temperature in the range when the transverse draw ratio is small. That is, the surface temperature of the film in the range where the transverse draw ratio is 2 to 3 times or less never falls below the surface temperature of the film in the range where the transverse draw ratio is 1 to 2 times or less, and the transverse draw ratio is 3 times. The surface temperature of the film in the above range does not fall below the surface temperature of the film in the range where the transverse draw ratio is 2 to 3 times or less.

In the transverse stretching step, the temperature increase rate of the surface temperature during stretching is preferably 60 ° C./min or less, more preferably 50 ° C./min or less, and even more preferably 40 ° C./min or less.
In the transverse stretching step, when the temperature increase rate of the surface temperature during stretching is 60 ° C./min or less, the molecular chain is prevented from moving rapidly during stretching, and the shear plane normal stress and shear plane yield stress are too low. It is suppressed. In addition, Re, which is effective in suppressing rainbow unevenness, is sufficiently increased, making it difficult to visually recognize rainbow unevenness.

<Heat setting>
It includes a heat setting step in which the polyester film after transverse stretching is heat-set by heating to the maximum temperature in the transverse stretching apparatus. Here, the maximum temperature in heat setting refers to the highest point of the film surface temperature reached by the film in the heat setting zone. It can be obtained by actually measuring the film surface temperature in the heat setting zone with a radiation thermometer.
After stretching, a heat treatment called “heat setting” is performed to promote crystallization. By performing a heat setting step of heating at a temperature exceeding the stretching temperature, crystallization can be promoted and the strength of the film can be increased.
In heat setting, the polyester film shrinks in volume due to crystallization.
As a heat fixing method, several slits for sending hot air to the extending portion are provided in parallel to the width direction. This can be achieved by making the temperature of the gas blown out from the slit higher than the stretched portion.
Further, a heat source (IR heater, halogen heater, etc.) may be installed near the exit of the stretching (part) to raise the temperature.

The maximum surface temperature of the polyester film in the heat setting step is preferably 130 ° C to 230 ° C, more preferably 150 ° C to 210 ° C, and still more preferably 160 ° C to 200 ° C.
If the maximum surface temperature in the heat setting process is 130 ° C or higher, the shear surface normal stress and the shear surface yield stress are prevented from excessively decreasing, and if it is 230 ° C or lower, the shear surface normal stress and shear surface yield stress increase. Too much is suppressed.

  The heating rate of the film from the end of the stretching process to the maximum temperature in the heat setting process is preferably 1000 ° C./min or less, more preferably 800 ° C./min or less, and still more preferably 700 ° C./min or less.

  If the heating rate of the film in the heat setting process from the end of the stretching process is 1000 ° C./min or less, the rapid relaxation of molecules before crystallization is suppressed, and the shear plane normal stress and shear plane yield stress are reduced. It is possible to prevent the rainbow unevenness from being overlooked or Re not sufficiently increased.

The time when the surface temperature exceeds 130 ° C. is preferably 180 seconds or shorter, more preferably 120 seconds or shorter, and even more preferably 60 seconds or shorter.
If the surface temperature exceeds 130 ° C. for 180 seconds or less, crystallization does not proceed excessively, the shear plane normal stress and the shear plane yield stress increase excessively, or Rth increases excessively and rainbow unevenness is visually recognized. It is suppressed.

<Heat relaxation>
It is preferable to include a heat relaxation step of heating the polyester film after the heat setting step and narrowing the length of at least the film transport direction (MD) and the direction (TD) perpendicular to the film transport direction of the polyester film.
The heat relaxation step is not strictly limited to an embodiment performed after the heat setting step, and the heat setting step and the heat relaxation step may be performed simultaneously. When performing the heat setting step and the heat relaxation step at the same time, the heat setting step can be performed until the maximum temperature in the transverse stretching apparatus is reached, and the heat relaxation can be continued at a temperature not exceeding the maximum temperature in the transverse stretching apparatus. it can.
After the heat setting step, it is preferable to relax (shrink the film) simultaneously with the heat treatment, both in the TD direction (direction orthogonal to the film transport direction: also referred to as the horizontal direction) and MD (film transport direction: also referred to as the vertical direction). It is preferable to relax.

Narrowing the length of the polyester film in the heat relaxation process in the direction orthogonal to the film transport direction includes narrowing the distance between the pair of rails installed on both sides of the film transport path, and the polyester film in the heat relaxation process. Preferably, reducing the length in the film transport direction includes narrowing the interval between the plurality of traveling clips.
In MD direction, before releasing the polyester film after transverse stretching from the clip, in addition to the heat setting step of heating the polyester film after transverse stretching to the maximum temperature in the transverse stretching apparatus, it was installed on both sides of the film conveyance path. It is preferable to include narrowing the interval between the plurality of clips that respectively travel along the pair of rails.
Mitigation by narrowing the gap between clips can be achieved, for example, by using a pantograph-like chuck for the tenter and narrowing the gap between the pantographs, or by driving the clip on an electromagnet and reducing the drive speed. it can.

Shrinking the length of the polyester film in the film transport direction in the heat relaxation step can be performed by applying a tension in the film transport direction of the polyester film and shortening the length while transporting it under heating conditions.
The film length can be shortened during heating by applying a tension below the residual stress of the film to the polyester film while conveying the polyester film under heating conditions. By applying tension to the polyester film under heating conditions, the polyester film shrinks during heating due to residual stress, so the length in the film transport direction can be shortened. The residual stress of the polyester film can be determined, for example, by measuring the shrinkage force of the film during heating using a thermomechanical analyzer (TMA-60, manufactured by Shimadzu Corporation).

Setting the relaxation rate of TD, which is the rate of narrowing the TD length of the heat-fixed polyester film, to 0.1% to 7.0% further improves the scratch resistance of the polyester film and suppresses the thermal shrinkage rate It is preferable from a viewpoint to do, 0.5 to 5.0% is more preferable, and 1.0 to 4.0% is further more preferable. When the TD relaxation rate is 0.1% or more, the thermal shrinkage rate can be reduced, and when the TD relaxation rate is 7% or less, TD is less likely to be loosened during the relaxation process. The occurrence of surface failures such as wrinkles and scratches is preferably suppressed.
In the thermal relaxation process, the MD relaxation rate, which is the ratio of shrinking the MD length of the heat-fixed polyester film, is preferably 0.1% to 7%, more preferably 0.5% to 5.0%. Preferably, 1.0% to 4.0% is more preferable. When the relaxation rate of MD is 0.1% or more, the thermal shrinkage rate of MD can be reduced, and the decorative layer is peeled off during the punching process of the decorative film obtained using the polyester film, or the film is deformed. Is less likely to occur. When the MD relaxation rate is 7% or less, it is difficult to cause looseness in the MD during the relaxation treatment, and the occurrence of planar failures such as wrinkles and scratches is suppressed, which is preferable.

  As a preferable condition in the thermal relaxation process for suppressing the thermal shrinkage rate of the polyester film to 3.0% or less, the conveyance tension of the polyester film in the thermal relaxation process is in the range of 10 N / m width to 80 N / m width, 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. During cooling after narrowing the length of the polyester film, the film surface of the polyester film The cooling rate in the temperature range of 70 ° C. ± 20 ° C. may be 100 ° C./min to 2000 ° C./min.

  The conveyance tension of the polyester film in the thermal relaxation step is preferably in the range of 10 N / m width to 80 N / m width, more preferably in the range of 15 N / m width to 60 N / m width, and in the range of 20 N / m width to 40 N / m width. Is more preferable. When the transport tension is 10 N / m width or more, generation of scratches due to rubbing with the roller of the film in the thermal relaxation process is suppressed, and when the transport tension is 80 N / m width or less, the thermal shrinkage rate of the polyester film is reduced. The decorative layer is peeled off when a decorative film obtained using a polyester film is punched out, and deformation of the film after decoration is suppressed.

The relaxation temperature is low even at the same temperature as the heat setting (that is, even when the maximum temperature in the transverse stretching apparatus is reached) as long as the heat setting can be performed by heating the stretched polyester film to the maximum temperature in the stretching apparatus. It doesn't matter. Here, the maximum temperature in 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 actually measuring the film surface temperature in the thermal relaxation zone with a radiation thermometer.
Especially, the film surface temperature of the film during the heat treatment in the thermal relaxation step is preferably 110 ° C to 190 ° C, more preferably 120 ° C to 175 ° C, and further preferably 120 ° C to 160 ° C. When the film surface temperature is 110 ° C. or higher, the thermal shrinkage rate of the polyester film can be reduced, and the decorative layer is peeled off when the decorative film obtained using the polyester film is punched, Film deformation is suppressed. When the film surface temperature is 190 ° C. or lower, the occurrence of failures such as wrinkling of the film in the relaxation process is suppressed.

  The heat treatment time in the thermal relaxation step is preferably 10 seconds to 600 seconds, more preferably 30 seconds to 300 seconds, and still 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 decorative layer is peeled off when the decorative film obtained using the polyester film is punched and processed. Film deformation is suppressed. When the heat treatment time is 600 seconds or less, occurrence of planar failures such as wrinkles of the film in the thermal relaxation process is suppressed.

<Cooling>
It is preferable to include a step of cooling the polyester film before releasing the polyester film after heat setting or heat relaxation from the clip. The polyester film after heat setting or heat relaxation is preferably cooled before being released from the clip from the viewpoint of easily reducing the temperature of the clip when the polyester film is released from the clip.
The cooling temperature of the polyester film after heat setting or heat relaxation is preferably 80 ° C. or less, more preferably 70 ° C. or less, and particularly preferably 60 ° C. or less.
Specific examples of the method for cooling the polyester film after heat setting include a method in which cold air is applied to the polyester film.
When cooling after the thermal relaxation step, the film cooling rate in the range of the film surface temperature of 70 ° C. ± 20 ° C. is preferably 100 ° C./min to 2000 ° C./min, and 300 ° C./min to 1500 ° C./min. More preferably, 500 ° C./min to 1000 ° C./min is more preferable.
When the cooling rate is 100 ° C./min or more, the transport distance in the cooling zone becomes appropriate, which is preferable in terms of the apparatus size and cost. Moreover, generation | occurrence | production of planar failures, such as a wrinkle at the time of cooling of a polyester film, is suppressed because a cooling rate is 2000 degrees C / min or less.

  The temperature control means for heating or cooling the polyester film in preheating, stretching, heat setting, heat relaxation, and cooling in the production of the polyester film may be performed by blowing warm air or cold air on the polyester film, polyester For example, the film may be brought into contact with the surface of a metal plate whose temperature can be controlled, or the film may be passed in the vicinity of the metal plate.

  By performing the above-described preheating step, transverse stretching step, heat setting step, and heat relaxation step, the preferred thermal shrinkage, Re, Rth, and Re / Rth of the polyester film can be easily achieved. It is easy to produce a polyester film that can exhibit effects such as reduction and curling suppression of a decorative film created using the polyester film.

<Release film from clip>
After the above process, the polyester film is released from the clip.
It is preferable to control the surface temperature of the polyester film when the polyester film is detached from the clip in the range of 40 ° C to 140 ° C. The surface temperature of the polyester film when the polyester film is detached from the clip is more preferably 50 ° C. or more and 120 ° C. or less, and further preferably 60 ° C. or more and 100 ° C. or less.

  In the method for producing a polyester film, the thickness of the polyester film after film formation is complete (after the step of releasing from the clip) is from 40 μm to 500 μm, more preferably from 60 μm to 400 μm, and even more preferably from 80 μm to 300 μm. By setting the thickness of the polyester film in the above range, the decorative film having the polyester film as a base material has sufficient rigidity, and the punching property and the handling property due to the rigidity being too strong are suppressed, Dimensional stability becomes better.

<Recovery, slitting and winding of film>
After release from the clip, the film is trimmed, slit, and thickened as necessary and wound up for collection.
In the production method of the polyester film, the film width after being released from the clip is preferably 0.8 to 6 m from the viewpoint of efficiently securing the film product width and the size of the apparatus is not excessive, and is 1 to 5 m. Is more preferable, and it is especially preferable that it is 1 m-4 m. An optical film requiring accuracy is usually formed with a thickness of less than 3 m, but in the present embodiment, it is preferable to form with a width as described above.
In addition, the film formed into a wide film may be slit to preferably 2 or more and 6 or less, more preferably 2 or more and 5 or less, and further preferably 3 or more and 4 or less, and then wound.

After slitting, it is preferable to process the thickness at both ends (knurling).
The winding is preferably performed at a diameter of not less than 1000 m and not more than 10000 m on a core having a diameter of not less than 70 mm and not more than 600 mm. Winding tension per cross-sectional area of the film is ^{preferably 30N / cm 2 ~300N / cm 2} , more preferably ^{50N / cm 2 ~250N / cm 2} , even more preferably at ^70N / cm ^{2 ~200N} / cm 2 . It is also preferable to bond a masking film before winding.

[Hard coat layer]
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. When the hard coat layer is disposed on the outermost surface, the scratch resistance is improved. From the viewpoint of further improving the scratch resistance, the pencil hardness of the hard coat layer surface is preferably H or more, more preferably 3H or more, and more preferably 5H or more. preferable.

<Hard coat layer>
Hereinafter, the hard coat layer in the decorative film of the present disclosure will be described.
The hard coat layer may be formed by either a wet coating method or a dry coating method (vacuum film formation), but is preferably formed by a wet coating method having excellent productivity.
As the hard coat layer, for example, JP 2013-45045 A, JP 2013-43352 A, JP 2012-232459 A, JP 2012-128157 A, JP 2011-131409 A, JP JP2011-131404A, JP2011-126162A, JP2011-75705A, JP2009-286981, JP2009-263567, JP2009-75248, JP2007-. No. 164206, JP-A No. 2006-96811, JP-A No. 2004-75970, JP-A No. 2002-156505, JP-A No. 2001-272503, WO12 / 018087, WO12 / 098967, WO12 / 0886659, WO11 / Described in 105594 The Dokoto layer can be used.

(Thickness of hard coat layer)
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 having good scratch resistance can be obtained.
From the viewpoint of further improving the scratch resistance, the thickness of the hard coat layer is more preferably 10 μm or more, and further preferably 15 μm or more.
The thickness of the hard coat layer is preferably 40 μm or less, more preferably 35 μm or less, from the viewpoint that punching can be easily performed.

(Constituent material of hard coat layer)
The hard coat layer includes at least a structure derived from the following a), a structure derived from the following b), the following c) and the following d),
When the hard coat layer is 100% by mass of the total solid content of the hard coat layer,
15% by mass to 70% by mass of the structure derived from the following a),
25% by mass to 80% by mass of the structure derived from b) below,
The following c) is 0.1% by mass to 10% by mass,
It is preferable to contain 0.1 mass%-10 mass% of following d).
a) a compound having one alicyclic epoxy group and one group containing an ethylenically unsaturated double bond in the molecule and having a molecular weight of 300 or less; b) three or more ethylenic groups in the molecule. Compound having a group containing a saturated double bond c) Radical polymerization initiator d) Cationic polymerization initiator By providing a hard coat layer having such a configuration, the decorative film has high pencil hardness and excellent smoothness. The film appearance change after wet heat aging is suppressed.

(Configuration of hard coat layer)
It is preferable that the hard coat layer has a configuration formed by a coating method on at least one surface of the polyester film according to the above-described embodiment.
The hard coat layer is formed by curing a composition for forming a hard coat layer including a), b), c) and d), and the composition for forming a hard coat layer is the total solid of the composition for forming a hard coat layer. When the content is 100% by mass, a) is 15% by mass to 70% by mass, b) is 25% by mass to 80% by mass, c) is 0.1% by mass to 10% by mass, and d) is 0.1% by mass. More preferably, the content is 10% by mass to 10% by mass.

<Hardcoat layer and hardcoat layer forming composition>
Hereafter, the detail about each component contained in the composition for hard-coat layer and hard-coat layer formation is described.

-A) Compound having one alicyclic epoxy group and one ethylenically unsaturated double bond in the molecule, and a molecular weight of 300 or less-
A hard-coat layer contains 15 mass%-70 mass% of structures derived from the following a), when the total solid of a hard-coat layer is 100 mass%.
a) A compound having one alicyclic epoxy group and one ethylenically unsaturated double bond group in the molecule and having a molecular weight of 300 or less.
The hard coat layer is formed by curing a hard coat layer forming composition containing at least a), b), c) and d), and the hard coat layer forming composition is a hard coat layer forming composition. When the total solid content of the product is 100% by mass, a) is preferably contained in an amount of 15% to 70% by mass.

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

Examples of the group containing an ethylenically unsaturated double bond include polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group, and among them, a (meth) acryloyl group and —C (O). OCH═CH ₂ is preferable, and a (meth) acryloyl group is particularly preferable. By having a group containing an ethylenically unsaturated double bond, it is possible to maintain higher hardness and to impart heat and heat resistance.

  The number of groups containing an epoxy group and an ethylenically unsaturated double bond in the molecule is one. When each functional group is 1, the number of functional groups (groups containing an epoxy group and an ethylenically unsaturated double bond) is reduced as compared to the case of 2 or more, thereby reducing the molecular weight and pencil hardness. This is because it becomes higher.

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

  The component a) is not limited as long as it has one alicyclic epoxy group and one ethylenically unsaturated double bond group in the molecule and has a molecular weight of 300 or less. It is preferable that it is a compound represented by 5).

Formula (5)

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

When R in Formula (5) is a monocyclic hydrocarbon, it is preferably an alicyclic hydrocarbon, more preferably an alicyclic group having 4 to 10 carbon atoms, and an alicyclic group having 5 to 7 carbon atoms. Group is more preferable, and an alicyclic group having 6 carbon atoms is particularly preferable. Specifically, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group are preferable, and a cyclohexyl group is particularly preferable.
In the case where R in the formula (5) is a bridged hydrocarbon, a bicyclic bridge (bicyclo ring) or a tricyclic bridge (tricyclo ring) is preferable, and examples thereof include a bridged hydrocarbon having 5 to 20 carbon atoms, and a norbornyl group Bornyl group, isobornyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group, tricyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like.
When L represents a divalent linking group, a divalent aliphatic hydrocarbon group is preferred. As a bivalent aliphatic hydrocarbon group, 1-6 are preferable, as for carbon number, 1-3 are more preferable, and 1 is still more preferable. 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) acryloyl group, vinyl group, styryl group, and allyl group. Among them, (meth) acryloyl group and —C (O) OCH═CH ₂ are preferable and particularly preferable. Is a (meth) acryloyl group.

As a specific compound of component a), a compound having one alicyclic epoxy group and one group containing an ethylenically unsaturated double bond in the molecule and having a molecular weight of 300 or less Although not specifically limited, the compound described in paragraph [0015] of JP-A-10-17614, a compound represented by the following formula (1A) or (1B), 1,2-epoxy-4-vinylcyclohexane, or the like is used. Can do.
Among these, a compound represented by the following formula (1A) or formula (1B) is more preferable, and a compound represented by the following formula (1A) having a low molecular weight is more preferable. In addition, the compound represented by the following formula (1A) is also preferably an isomer thereof. In the formula of the following formula (1A), L ₂ represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and the component having 1 carbon atom (that is, a) is epoxycyclohexylmethyl. (Meth) acrylate) is more preferable from the viewpoint of improving smoothness.
By using these compounds, both high pencil hardness and excellent smoothness can be achieved at a higher level.

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

In 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 represented by L _{2 in} the formulas (1A) and (1B) has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 carbon atom. 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.

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

-B) Compound having a group containing 3 or more ethylenically unsaturated double bonds in the molecule-
The hard coat layer according to the present disclosure includes 25% by mass to 80% by mass of the structure derived from the following b) when the total solid content of the hard coat layer is 100% by mass.
b) A compound having a group containing 3 or more ethylenically unsaturated double bonds in the molecule.
The hard coat layer is formed by curing a hard coat layer forming composition containing at least a), b), c) and d), and the hard coat layer forming composition is a hard coat layer forming composition. When the total solid content of the product is 100% by mass, it is preferable to contain 25 to 80% by mass of b).

The compound having a group containing 3 or more ethylenically unsaturated double bonds in the molecule b) contained in the composition for forming a hard coat layer will be described. b) A compound having a group containing three or more ethylenically unsaturated double bonds in the molecule is also referred to as “component b”.
The component b) can express higher hardness by having a group containing 3 or more ethylenically unsaturated double bonds in the molecule.
Examples of the component b) include esters of polyhydric alcohol and (meth) acrylic acid, vinylbenzene and its derivatives, vinyl sulfone, (meth) acrylamide, and the like.
Among these, from the viewpoint of hardness, a compound having 3 or more (meth) acryloyl groups is preferable, and examples thereof include acrylate compounds that form a hardened cured product widely used in the art.

  An example of such a compound is an ester of a polyhydric alcohol and (meth) acrylic acid having a group containing 3 or more ethylenically unsaturated double bonds in the molecule. For example, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (Meth) acrylate, EO-modified tri (meth) acrylate phosphate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, (di) pentaerythritol penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, poly Letane polyacrylate, polyester polyacrylate, caprolactone-modified tris (acryloxyethyl) isocyanurate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, Etc.

Furthermore, a resin (oligomer or prepolymer) having 3 or more (meth) acryloyl groups, a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups, and a urethane (meth) acrylate are also preferable.
Examples of the resin (oligomer or prepolymer) having three or more (meth) acryloyl groups include polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, and polythiol. Examples include oligomers or prepolymers such as polyene resins and polyfunctional compounds such as polyhydric alcohols.
Specific examples of polyfunctional (meth) acrylates having three or more (meth) acryloyl groups include dipentaerythritol hexaacrylate (DPHA) and the like, and the exemplified compounds shown in paragraph 0096 of JP-A-2007-256844 Can be mentioned.
Specific examples of the polyfunctional acrylate compound having three or more (meth) acryloyl groups include KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, TPA-330, and RP manufactured by Nippon Kayaku Co., Ltd. -1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, Osaka Organic Chemical Industry Co., Ltd. V # 400, V # 36095D and other polyols and (meth) acrylic An acid esterified product can be mentioned. Moreover, purple light 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 (DI EB-1290K, EB-220, EB-5129, EB-1830, EB-4358 (manufactured by Daicel UCB), Hicorp AU-2010, AU-2020 (manufactured by Tokushi Corporation), Aronix M-1960 (manufactured by Toa Gosei Co., Ltd.), Art Resin UN-3320HA, UN-3320HC, UN-3320HS, UN-904, HDP-4T and other trifunctional urethane acrylate compounds, Aronix M-8100, M A tri- or higher functional polyester compound of -8030, M-9050 (manufactured by Toagosei Co., Ltd., KBM-8307 (manufactured by Daicel Cytec Co., Ltd.)) and the like can also be suitably used.
Further, the component b) may be composed of a single compound or a combination of a plurality of compounds.

The structure derived from b) is contained in an amount of 25% by mass to 80% by mass when the total solid content of the hard coat layer is 100% by mass.
The component b) is contained in an amount of 25% by mass to 80% by mass when the total solid content of the hard coat layer forming composition is 100% by mass. Sufficient hardness can be obtained when the content of the structure derived from b) or the content of the component b) is 25% by mass or more with respect to the hard coat layer or the hard coat layer forming composition. On the other hand, when the content of the b) derived structure or b) component is 80% by mass or less with respect to the hard coat layer or the hard coat layer forming composition, the a derived structure or the content of the a) component is Since it decreases, smoothness is sufficient.
When the total solid content of the hard coat layer is 100% by mass, the structure derived from b) is preferably contained in an amount of 40% to 75% by mass, more preferably 60% to 75% by mass. preferable. When the total solid content of the composition for forming a hard coat layer is 100% by mass, the component b) is preferably contained in an amount of 40% to 75% by mass, and 60% to 75% by mass. Is more preferable.

-Other curable compounds-
The composition for forming a hard coat layer may contain a curable compound other than the component a) and the component b) (hereinafter also referred to as “other curable compound”). As other curable compounds, various compounds having a polymerizable group that can be cured (polymerized) by a curing treatment can be used. Examples of the polymerizable group include a polymerizable group capable of undergoing a polymerization reaction upon irradiation with light, an electron beam, or radiation, and a polymerizable group capable of undergoing a polymerization reaction upon heating, and a photopolymerizable group is preferred. Other curable compounds can be monomers, oligomers, prepolymers, and the like.

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

Specific examples of other curable compounds that can be contained in the composition for forming a hard coat layer include the following compounds.
(Meth) acrylic diesters of alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate; triethylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate diesters of polyoxyalkylene glycols such as (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate; (meth) of polyhydric alcohols such as pentaerythritol di (meth) acrylate Acrylic acid diesters; Ethylene such as 2,2-bis {4- (acryloxydiethoxy) phenyl} propane, 2,2-bis {4- (acryloxypolypropoxy) phenyl} propane Of N'okishido or propylene oxide adduct (meth) acrylic acid diesters; urethane (meth) acrylates, polyesters (meth) acrylates; isocyanuric acid acrylates, epoxy (meth) acrylates.

  As the urethane (meth) acrylate, for example, an alcohol, a polyol, and / or a hydroxyl group-containing compound such as a hydroxyl group-containing acrylate is reacted with an isocyanate, or, if necessary, a polyurethane compound obtained by these reactions ( Mention may be made of urethane (meth) acrylates obtained by esterification with (meth) acrylic acid. Specific examples include various commercially available products listed in paragraph 0017 of JP-A-2007-256844.

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

  From the viewpoint of the hardness of the hard coat layer, the content of the other curable compound with respect to the total solid content of the hard coat layer forming composition is determined when the total solid content of the hard coat layer forming composition is 100% by mass. 15% by mass or less, preferably 10% by mass or less, more preferably 1% by mass or less, still more preferably 0.01% by mass or less, substantially including It is particularly preferred not to.

-C) Radical polymerization initiator-
The hard coat layer according to the present disclosure contains 0.1% by mass to 10% by mass of c) radical polymerization initiator when the total solid content of the hard coat layer is 100% by mass.
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”.
Polymerization of the compound having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical polymerization initiator or a thermal radical polymerization initiator.
Commercially available compounds can be used as the photo- and thermal polymerization initiators, and they are described in “Latest UV Curing Technology” (p. 159, publisher: Kazuhiro Takahisa, publisher; Technical Information Association, 1991). Issued) or in the catalog of Ciba Specialty Chemicals Co., Ltd.
Specifically, as the component c), an alkylphenone photopolymerization initiator (Irgacure 651, Irgacure 184, DAROCURE 1173, Irgacure 2959, Irgacure 127, DAROCURE MBF, Irgacure 907, Irgacure 369, Irgacure 369, Irgacure 369, Irgacure 369, Irgacure 369, Irgacure 369 Photopolymerization initiator , LUCIRIN TPO) and others (Irgacure 784, Irgacure OXE01, Irgacure OXE02, Irgacure 754) and the like can be used.

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

-D) Cationic polymerization initiator-
The hard coat layer according to the present disclosure contains 0.1% by mass to 10% by mass of d) a cationic polymerization initiator when the total solid content of the hard coat layer is 100% by mass.
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 component d), a known compound such as a photoinitiator for cationic photopolymerization, a photodecoloring agent for dyes, a photochromic agent, a known acid generator used in a microresist or the like, and a mixture thereof Etc.
Examples thereof include onium compounds, organic halogen compounds, and disulfone compounds. Specific examples of these organic halogen compounds and disulfone compounds include the same compounds as those described above for the compounds that generate radicals.

  Examples of the onium compounds include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, selenonium salts, and the like. For example, paragraph numbers [0058] to [0059] And the like.

  In the present disclosure, particularly preferable cationic polymerization initiators include onium salts, and diazonium salts, iodonium salts, sulfonium salts, and iminium salts are suitable for photopolymerization initiation photosensitivity, compound material stability, etc. In terms of light resistance, iodonium salts are most preferable.

  Specific examples of onium salts that can be suitably used in the present disclosure include, for example, an amylated sulfonium salt described in paragraph [0035] of JP-A-9-268205, and JP-A-2000-71366. A diaryl iodonium salt or a triarylsulfonium salt described in paragraphs [0010] to [0011], a sulfonium salt of thiobenzoic acid S-phenyl ester described in paragraph [0017] of JP-A-2001-288205, Examples thereof include the onium salts described in paragraph numbers [0030] to [0033] of JP-A-2001-133696.

  Other examples include organometallic / organic halides described in JP-A-2002-29162, paragraphs [0059] to [0062], photoacid generators having o-nitrobenzyl type protecting groups, photolysis And compounds that generate sulfonic acid (iminosulfonate, etc.).

  Specific compounds of the iodonium salt-based cationic polymerization initiator include B2380 (manufactured by Tokyo Chemical Industry), BBI-102 (manufactured by Midori Chemical), WPI-113 (manufactured by Wako Pure Chemical Industries), and WPI-124 (manufactured by Wako Pure Chemical Industries). Industry-made), WPI-169 (made by Wako Pure Chemical Industries), WPI-170 (made by Wako Pure Chemical Industries), DTBPI-PFBS (made by Toyo Gosei) can be used.

  Furthermore, the following compounds FK-1 and FK-2 can be mentioned as preferable examples of the iodonium salt-based cationic polymerization initiator.

Photocationic polymerization initiator (iodonium salt compound) FK-1

Photocationic polymerization initiator (iodonium salt compound) FK-2

As a component d), only 1 type may be used and 2 or more types may be used together.
The component d) is added in the range of 0.1% by mass to 10% by mass, preferably 0.5% by mass, when the total solid content of the hard coat layer or the hard coat layer forming composition is 100% by mass. % To 3.0% by mass can be added. When the addition amount is in the above range, it is preferable from the viewpoint of stability of the curable composition, polymerization reactivity and the like.

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

-E) Inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond-
It is preferable to add e) inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond to the hard coat layer or the hard coat layer forming composition. Hereinafter, e) inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond are also referred to as “e) component”.
Since the amount of curing shrinkage of the hard coat layer (cured layer) can be reduced by adding inorganic particles, smoothness can be improved. Furthermore, pencil hardness can be improved by using inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond.
Examples of inorganic particles include silica particles, titanium dioxide particles, zirconium oxide particles, and aluminum oxide particles. Among them, e) inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond are preferably silica particles.

In general, since inorganic particles have low affinity with organic components such as polyfunctional vinyl monomers, they may form aggregates or the hard coat layer after curing may be easily cracked by simply mixing them. Therefore, in the component e), in order to increase the affinity between the inorganic particles and the organic component, it is preferable to treat the surface of the inorganic particles with a surface modifier containing an organic segment.
The surface modifier is preferably a surface modifier having a functional group capable of forming a bond with an inorganic particle or adsorbing to the inorganic particle and a functional group having an affinity for an organic component in the same molecule. Examples of the surface modifier having a functional group capable of binding or adsorbing to the inorganic particles include metal alkoxide surface modifiers such as silane, aluminum, titanium, and zirconium, or phosphoric acid groups, sulfuric acid groups, sulfonic acid groups, and carboxylic acid groups. A surface modifier having an anionic group is preferred. Furthermore, the functional group having an affinity with the organic component may be a functional group that is simply combined with the organic component and hydrophilicity / hydrophobicity, but a functional group that can be chemically bonded to the organic component is preferable, and in particular, an ethylenically unsaturated divalent group. A group containing a heavy bond or a ring-opening polymerizable group is preferred.
In the present disclosure, a preferable surface modifier for inorganic particles is a curable resin having a metal alkoxide or an anionic group and a group containing an ethylenically unsaturated double bond or a ring-opening polymerizable group in the same molecule. By chemically combining with the organic component, the crosslink density of the hard coat layer is increased, and the pencil hardness can be increased.

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

  The surface modification of these inorganic particles is preferably performed in a solution. When inorganic particles are mechanically finely dispersed, a surface modifier is present together, or after finely dispersing the inorganic particles, the surface modifier is added and stirred, or before the inorganic particles are finely dispersed. Alternatively, the surface may be modified (if necessary, heated, dried and then heated, or changed in pH), and then finely dispersed. As the solution for dissolving the surface modifier, an organic solvent having a large polarity is preferable. Specific examples include known solvents such as alcohols, ketones and esters.

The addition amount of the component e) is 5% by mass to 40% when the total solid content of the hard coat layer or the hard coat layer forming composition is 100% by mass in consideration of the balance between hardness and brittleness of the coating film. % By mass is preferable, and 10% by mass to 30% by mass is more preferable.
The size (average primary particle size) of the inorganic particles is preferably 10 nm to 100 nm, and more preferably 10 nm to 60 nm. The average particle diameter of the particles can be determined from an electron micrograph. If the particle size of the inorganic particles is equal to or greater than the lower limit value, an effect of improving the hardness is obtained, and if the particle size is equal to or smaller than the upper limit value, an increase in haze can be suppressed.
The shape of the inorganic particles may be either spherical or non-spherical, but a non-spherical shape in which 2 to 10 inorganic particles are connected is preferable from the viewpoint of imparting hardness. It is presumed that by using inorganic particles in which several particles are linked in a chain, a firm particle network structure is formed and the hardness is improved.
Specific examples of the inorganic particles include ELECOM V-8802 (spherical silica particles having an average primary particle size of 12 nm manufactured by JGC Corporation), ELECOM V-8803 (modified silica particles manufactured by JGC Corporation), MiBK- SD (spherical silica particles having an average primary particle size of 10 to 20 nm manufactured by Nissan Chemical Industries, Ltd.), MEK-AC-2140Z (spherical silica particles having an average primary particle size of 10 to 20 nm manufactured by Nissan Chemical Industries, Ltd.), MEK-AC-4130 (spherical silica particles having an average primary particle size of 40 to 50 nm manufactured by Nissan Chemical Industries, Ltd.), MiBK-SD-L (spherical particles having an average primary particle size of 40 to 50 nm manufactured by Nissan Chemical Industries, Ltd.) Silica particles), MEK-AC-5140Z (spherical silica particles having an average primary particle size of 70 nm to 100 nm manufactured by Nissan Chemical Industries, Ltd.) and the like. Among these, odd-shaped ELECOM V-8803 is preferable from the viewpoint of imparting surface hardness.

-F) Polyester urethane-
The hard coat layer or the hard coat layer forming composition in the present disclosure preferably contains f) polyester urethane from the viewpoint of increasing brittleness. Hereinafter, f) polyester urethane is also referred to as “f) component”.
Polyester urethane is 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 polyester urethane having a tensile strength of 25 MPa or more and a tensile elongation of 200% or more can contribute to increasing the hardness of the hard coat layer and imparting appropriate flexibility. It is inferred that this contributes to increasing the hardness and improving brittleness of the hard coat layer.
Moreover, if the polyester urethane content is 1 part by mass or more with respect to 100 parts by mass of the solid content of the hard coat layer or the composition for forming a hard coat layer, the above-described effect due to the addition of the polyester urethane can be sufficiently obtained. The hardness of the cured layer can be maintained as long as it is at most parts. Therefore, the polyester urethane content with respect to 100 parts by mass of the solid content of the hard coat layer or the hard coat layer forming composition is in the range of 1 part by mass to 10 parts by mass. From the viewpoint of improving brittleness and suppressing the 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.

  The use of polyester urethane exhibiting the above tensile strength and tensile elongation as the polyester urethane contributes to achieving both high hardness and improved brittleness by imparting appropriate flexibility to the hard coat layer. More preferably, the tensile strength is 40 MPa or more, and further preferably 50 MPa or more. Moreover, it is preferable that a tensile strength is 70 Mpa or less from a viewpoint of the compatibility stability in the composition for hard-coat layer formation. On the other hand, the tensile elongation is preferably 450% or more, and more preferably 600% or more. Further, from the viewpoint of securing pencil hardness, which is one of the indices of film hardness, the tensile elongation is preferably 1000% or less. About the measuring method of pencil hardness, an Example is mentioned later. The tensile strength and tensile elongation of the polyester urethane are values measured using a tensile strength tester according to JIS K 6251.

Polyester urethane can be obtained by polymerization of monomer components containing at least diol, dicarboxylic acid, and diisocyanate. As the three types of monomers described above, 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, respectively. Is preferred.
The hydrocarbon group having an unbranched structure is preferably an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof.
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 to 8, more preferably 2 to 6, and still more preferably 2 to 4. .
The arylene group may have an alkyl group having 1 to 8 carbon atoms as a substituent.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a p-phenylene group.
As the hydrocarbon group, the alkylene group, the arylene group, or a combination thereof is particularly preferable.

Examples of diols used as polyester urethane monomers include ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and 1,5- Pentanediol is preferred.
As the dicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, oxalic acid and malonic acid are preferable.
Diisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate, p, p'-diphenylmethane diisocyanate and 1,5-naphthyl. Range isocyanate is preferred.

  The number average molecular weight (Mn) of the polyester urethane is preferably 5000 or more from the viewpoint of affinity with inorganic particles, preferably 10,000 or more, and 50,000 or less from the viewpoint of compatibility with the curable compound. It is preferable that

  Moreover, in one aspect | mode, the polyester urethane may have a reactive group. The reactive group is preferably a polymerizable unsaturated group. About a specific example, it is as having described about the functional group which an inorganic particle may have previously.

  As polyester urethane demonstrated above, the polyester urethane synthesize | combined by the well-known method may be used, and a commercial item may be used. Examples of commercially available products include Byron (registered trademark) series (trade name): manufactured by Toyobo Co., Ltd., Byron UR-2300, Byron UR-3200, Byron UR-3210, Byron UR-3260, Byron UR-5537. 300 Byron UR-8300, Byron UR-8700 and the like can be preferably used.

-G) Antifouling agent-
It is preferable that the hard coat layer or the composition for forming a hard coat layer in the present disclosure contains g) an antifouling agent because adhesion of fingerprints and dirt is reduced and wiping off the attached dirt is simplified. Moreover, it is also preferable from the viewpoint of improving the scratch resistance by improving the slip property of the surface. Hereinafter, g) antifouling agent is also referred to as “g) component”.
In the hard coat layer according to the present disclosure, g) the antifouling agent contains a fluorine-containing compound, the fluorine-containing compound contained has a perfluoropolyether group and a polymerizable unsaturated group, and is polymerizable unsaturated. It is preferable to have a plurality of groups in one molecule.
The g) antifouling agent that can be used in the present disclosure will be described.

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

The fluorine-containing antifouling agent is considered to have the following effects (1) to (3) by having a polymerizable unsaturated group.
(1) Solubility in an organic solvent and compatibility with a compound having an unsaturated double bond increase, so that the antifouling agent can be uniformly localized on the surface without forming an aggregate. Conceivable. Moreover, generation | occurrence | production of the defect by an aggregate can be prevented.
(2) Even if the fluorine-containing antifouling agent is localized on the surface, it can form a covalent bond by photopolymerization reaction with the fluorine-containing antifouling agents or with a compound having an unsaturated double bond. Can be prevented, and the deterioration of the antifouling property can be prevented.
(3) It is possible to prevent the loss of antifouling property and the deterioration of the appearance due to the antifouling agent bleeding out and depositing.

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 capable of causing a radical polymerization reaction by irradiating active energy rays such as ultraviolet rays or electron beams, and includes (meth) acryloyl group, (meth) acryloyloxy group, vinyl. Groups, allyl groups, and the like, and (meth) acryloyl groups, (meth) acryloyloxy groups, and groups in which any hydrogen atom in these groups is substituted with a fluorine atom are preferably used.
As a specific example of the polymerizable unsaturated group, a group having the structure shown below is preferable.

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

The (per) fluoroalkyl group is preferably a group having 1 to 20 carbon atoms, more preferably a group having 1 to 10 carbon atoms.
The (per) fluoroalkyl group is a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H. Etc.) even in the branched structure (for example, 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 Or an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group or an alkyl group substituted with these).

The (per) fluoropolyether group refers to a case where the (per) fluoroalkyl group has an ether bond, and may be a monovalent or divalent group. Examples of the fluoropolyether group include —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, —CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , —CH ₂ CH _{2. OCF 2 CF 2 OCF 2 CF 2} H, fluorocycloalkyl group having 4 to 20 carbon atoms and having a fluorine atom 4 or more can be mentioned. As the perfluoropolyether group, for _{example, - (CF 2 O) p} - (CF 2 CF 2 O) q -, - [CF (CF 3) CF 2 O] p - [CF 2 (CF 3) _{] -, - (CF 2 CF} 2 CF 2 O) p -, - (CF 2 CF 2 O) p - , and the like.
The total of p and q is preferably 1 to 83, more preferably 1 to 43, and most preferably 5 to 23.
Fluorine-containing antifouling agent, from the viewpoint of excellent antifouling properties _{- (CF 2 O) p -} (CF 2 CF 2 O) q - and particularly preferably having a perfluoropolyether group represented by.
P and q each independently represent an integer of 0 to 20. However, p + q is an integer of 1 or more.

  From the viewpoint that the effects shown in the above (1) to (3) can be obtained more remarkably, the fluorine-containing antifouling agent has a perfluoropolyether group and contains a polymerizable unsaturated group in one molecule. It is preferable to have a plurality.

In the formula (F), W represents a linking group. Examples of W include an alkylene group, an arylene group, a heteroalkylene group, and a linking group obtained by combining these. These linking groups may further have a functional group such as an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, or a combination thereof.
W is preferably an ethylene group, more preferably an ethylene group bonded to a carbonylimino group.

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

  In the formula (F), when both n and m are 1, specific examples of the following preferred embodiments include the following formulas (F-1) to (F-3).

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

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

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

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

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

When telomerization is used in the synthesis of the compound represented by the above formula (F-1), the group Rf ² of the formula (F-1) may be used depending on the conditions of telomerization and the separation conditions of the reaction mixture. _{(CF 2 CF 2) p R} '2 CH 2 CH 2 R 2 O- p's k respectively, k + 1, k + 2 , may include a plurality of fluorinated (meth) acrylic acid esters such as ....

Formula (F-2):
_{F (CF 2) q -CH 2} -CHX-CH 2 Y
In formula (F-2), q is an integer of 1 to 20, X and Y are each independently either a (meth) acryloyloxy group or a hydroxyl group, and at least one is a (meth) acryloyloxy group.

The fluorine-containing (meth) acrylic acid ester represented by the formula (F-2) has a fluoroalkyl group having 1 to 20 carbon atoms having a trifluoromethyl group (CF _3- ) at the terminal. Even if a small amount of fluorine (meth) acrylate is used, the trifluoromethyl group is effectively oriented on the surface.

  In view of antifouling properties and ease of production, q is preferably 6 to 20, and more preferably 8 to 10. The fluorine-containing (meth) acrylic acid ester having a fluoroalkyl group having 8 to 10 carbon atoms is superior in water repellency and water repellency compared with other fluorine-containing (meth) acrylic acid esters having a fluoroalkyl group having a chain length. Because it exhibits oiliness, it has excellent antifouling properties.

  Specifically, as the fluorine-containing (meth) acrylic acid ester represented by the formula (F-2), 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-heneicosafluorotridecane, 2- (meth) acryloyloxy-1-hydroxy-4,4 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotridecane 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-heneico Examples include safluorotridecane. In the present disclosure, 1-acryloyloxy-2-hydroxy-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12, 13,13,13-heneicosafluorotridecane is preferred.

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 represents a hydrogen atom or a methyl group, s represents an integer of 1 to 20, and r represents an integer of 1 to 4.

  The fluorine atom-containing monofunctional (meth) acrylate represented by the formula (F-3) reacts a fluorine atom-containing alcohol compound represented by the following formula (FG-3) and a (meth) acrylic acid halide. Can be obtained.

Formula (FG-3):
_{F (CF 2) r O (} CF 2 CF 2 O) s CF 2 CH 2 OH
In formula (FG-3), s represents an integer of 1 to 20, and r represents an integer of 1 to 4.

Specific examples of the fluorine atom-containing alcohol compound represented by the formula (FG-3) include, for example, 1H, 1H-perfluoro-3,6-dioxaheptan-1-ol, 1H, 1H-perfluoro-3,6- Dioxaoctane-1-ol, 1H, 1H-perfluoro-3,6-dioxadecan-1-ol, 1H, 1H-perfluoro-3,6,9-trioxadecan-1-ol, 1H, 1H-perfluoro- 3,6,9-trioxaundecan-1-ol, 1H, 1H-perfluoro-3,6,9-trioxatridecan-1-ol, 1H, 1H-perfluoro-3,6,9,12-tetra Oxatridecan-1-ol, 1H, 1H-perfluoro-3,6,9,12-tetraoxatetradecan-1-ol, 1H, 1H-perfluoro 3,6,9,12-tetraoxahexadecan-1-ol, 1H, 1H-perfluoro-3,6,9,12,15-pentaoxahexadecan-1-ol, 1H, 1H-perfluoro-3,6 9,12,15-pentaoxaheptadecan-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-heptaoxatricosan-1-ol, 1H, 1H-perfluoro-3,6,9,12,15,18,21-hepta Kisapentakosan-1-ol, and the like can be given.
These are available on the market, and specific examples thereof include, for example, 1H, 1H-perfluoro-3,6-dioxaheptan-1-ol (trade name “C5GOL”, manufactured by Exfloor), 1H, 1H-perfluoro- 3,6,9-trioxadecan-1-ol (trade name “C7GOL”, manufactured by Exfloor), 1H, 1H-perfluoro-3,6-dioxadecan-1-ol (trade name “C8GOL”, Exfloor) 1H, 1H-perfluoro-3,6,9-trioxatridecan-1-ol (trade name “C10GOL”, manufactured by Exfloor), 1H, 1H-perfluoro-3,6,9,12 -Tetraoxahexadecan-1-ol (trade name “C12GOL”, manufactured by Exfloor) and the like.
In the present disclosure, 1H, 1H-perfluoro-3,6,9,12-tetraoxatridecan-1-ol is preferably used.

  Moreover, as a (meth) acrylic acid halide made to react with the fluorine atom containing alcohol compound represented by Formula (FG-3), (meth) acrylic acid fluoride, (meth) acrylic acid chloride, (meth) acrylic acid bromide, (Meth) acrylic acid iodide can be mentioned. From the viewpoint of easy availability, (meth) acrylic acid chloride is preferred.

  Although the preferable specific example of a compound represented by a formula (F-3) below is shown, it is not limited to these. In addition, the preferable specific example represented by Formula (F-3) has description also in Unexamined-Japanese-Patent 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

  In addition to the compound represented by the formula (F-3), a compound represented by the following formula (F-3A) can also be preferably used.

Formula (F-3A):
_{^{Rf 3 - [(O) c}} (O = C) b (CX 4 X 5) a -CX 3 = CX 1 X 2]
Wherein X ¹ and X ² each independently represent H or F, X ³ represents H, F, CH ₃ or CF ₃ , and X ⁴ and X ⁵ each independently represent H, F, or CF ₃ , a, b, and c each independently represent 0 or 1, and Rf ³ represents a fluorine-containing alkyl group containing an ether bond having 18 to 200 carbon atoms), and Rf ^{3 in the} group ,
Formula (FG-3A):
-(CX ⁶ ₂ CF ₂ CF ₂ O)-
A fluorine-containing unsaturated compound having 6 or more repeating units represented by (wherein X ⁶ is F or H).

As an example of the fluorine-containing polyether compound represented by the formula (F-3A),
_{^{(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]
As the polymerizable unsaturated group of the fluorine-containing polyether compound, a group having the following structure is preferable. The definition of each symbol in (c-1) to (c-3) is synonymous with the formula (FG-3A).

  Moreover, the fluorine-containing polyether compound represented by the formula (F-3A) may have a plurality of polymerizable unsaturated groups, and structures such as the following structures are preferred.

In the present disclosure, a compound having a structure of —O (C═O) CF═CH ₂ is preferable in that it has a particularly high polymerization (curing) reactivity and can efficiently obtain a cured product.

In the fluorine-containing polyether compound represented by the formula (F-3A), it is important that the Rf ³ group contains 6 or more fluorine-containing polyether chains of the formula (FG-3A) in Rf ^{3 as} repeating units. Yes, thereby imparting antifouling properties.
More specifically, it may be a mixture in which the repeating unit of the fluorine-containing polyether chain contains 6 or more compounds. However, when used in the form of a mixture, the fluorine-containing unsaturated compound having less than 6 repeating units and 6 In a distribution with one or more fluorine-containing unsaturated compounds, a mixture having the highest abundance ratio of the fluorine-containing unsaturated compounds having 6 or more polyether chain repeating units is preferable.
The number of repeating units 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 but also the antifouling property, in particular, the removability to soils containing oil components can be improved. Moreover, gas permeability can be imparted more effectively. Further, the fluorine-containing polyether chain may be present at the end of the Rf ³ group or in the middle of the chain.

Specifically, the Rf ³ group is:
Formula (c-4):
_{^{R 4 - (CX 6 2 CF}} 2 CF 2 O) t - (R 5) e -
(Wherein X ⁶ is the same as formula (FG-3A), R ⁴ is selected from a hydrogen atom, a halogen atom or an alkyl group, a fluorine-containing alkyl group, an alkyl group containing an ether bond and a fluorine-containing alkyl group containing an ether bond) And at least one kind, R ⁵ is a divalent or higher organic group, t is an integer of 6 to 66, and e is 0 or 1.
That is, it is a fluorine-containing organic group that is bonded to a reactive carbon-carbon double bond via a divalent or higher-valent organic group R ⁵ and further has R ⁴ at the terminal.
R ⁵ may be any organic group as long as it can bind the fluorine-containing polyether chain of the formula (FG-3A) to a reactive carbon-carbon double bond. For example, it is selected from an alkylene group, a fluorine-containing alkylene group, an alkylene group containing an ether bond and a fluorine-containing alkylene group containing an ether bond. Among these, a fluorine-containing alkylene group and a fluorine-containing alkylene group containing an ether bond are preferable in terms of transparency and low refractive index.

As specific examples of the fluorine-containing polyether compound represented by the formula (F-3A), compounds exemplified in WO2003 / 022906 pamphlet are 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), when n and m are not 1 at the same time, the following preferred embodiments include the formula (F-4) and the formula (F-5).

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

Rf ¹ may be a monovalent to trivalent group. When Rf ¹ is monovalent, terminal groups include (C _n F _{2n + 1} )-, (C _n F _{2n + 1} O)-, (XC _n F _2n O)-, (XC _n F _{2n + 1} )-(wherein X is It is preferably hydrogen, chlorine or bromine, and n is an integer of 1 to 10. Specifically _{CF 3 O (C 2 F 4} O) p CF 2 -, C 3 F 7 O (CF 2 CF 2 CF 2 O) p CF 2 CF 2 -, C 3 F 7 O (CF (CF 3 _{) CF 2 O) p CF (} CF 3) -, F (CF (CF 3) CF 2 O) p CF (CF 3) - and the like can be preferably used.

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

If Rf ¹ is a _{divalent, - (CF 2 O) q} (C 2 F 4 O) r CF 2 -, - (CF 2) 3 O (C 4 F 8 O) r (CF 2) 3 -, _{-CF 2 O (C 2 F 4} O) r CF 2 -, - C 2 F 4 O (C 3 F 6 O) r C 2 F 4 -, - CF (CF 3) (OCF 2 CF (CF 3) _{) s OC t F 2t O (} CF (CF 3) CF 2 O) r CF (CF 3) - and the like can be preferably used.

Here, the average value of q, r, and s is 0-50. Preferably it is 3-30, More preferably, it is 3-20, Most preferably, it is 4-15. t is an integer of 2-6.
A preferred specific example or synthesis method of the compound represented by the formula (F-4) is described in International Publication No. 2005/113690.

Hereinafter, a compound having an average value of p of 6 to 7 in F (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) — is referred to as “HFPO-”, and — (CF (CF ₃ ) CF _{2 O) p CF (CF 3} ) - a in the average value of p is 6-7 compounds described as "-HFPO-", shows the specific compounds of formula (F-4), but are not limited to.

_{(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): of _{HFPO-CONH-C 3 H 6} NHCH 3 trimethylolpropane triacrylate 1: 1 Michael addition polymers _{(d-4) :( CH 2} = CHCOOCH 2) 2 H-C-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, the compound represented by the following formula (F-5) can also be used as the compound represented by the formula (F-4).

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 C 2-20 fluoroalkyl group having 3 or more fluorine atoms or a carbon number having 4 or more fluorine atoms. 4 to 20 fluorocycloalkyl groups are shown.)

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

  Specific examples of the compound represented by the formula (F-5) include, for example, di (meth) acrylic acid-2,2,2-trifluoroethylethylene glycol, di (meth) acrylic acid-2,2,3. , 3,3-pentafluoropropylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,4-heptafluorobutylethylene glycol, di (meth) acrylic acid-2,2,3 , 3,4,4,5,5,5-nonafluoropentylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,6-undeca Fluorohexylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptylethylene glycol, di (meth) acrylic Acid-2, 2, 3, 3, 4 4,5,5,6,6,7,7,8,8,8-pentadecafluorooctylethylene glycol, di (meth) acrylic acid-3,3,4,4,5,5,6,6 7,7,8,8,8-tridecafluorooctylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8, 8,9,9,9-heptadecafluorononylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8, 9,9,10,10,10-nonadecafluorodecylethylene glycol, di (meth) acrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,9, 9,10,10,10-heptadecafluorodecylethylene glycol, di (meth) acrylic acid-2-trifluoromethyl -3,3,3-trifluoropropylethylene glycol, di (meth) acrylic acid-3-trifluoromethyl-4,4,4-trifluorobutylethylene glycol, di (meth) acrylic acid-1-methyl- Preferred examples include 2,2,3,3,3-pentafluoropropylethylene glycol and di (meth) acrylic acid-1-methyl-2,2,3,3,4,4,4-heptafluorobutylethylene glycol. It can be used alone or as a mixture. Such a di (meth) acrylic acid ester can be prepared by a known method as described in JP-A-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-heptadecafluorononylethylene glycol is preferred. Used.

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

The fluorine-containing antifouling agent in the present disclosure may be any of a monomer, an oligomer, or a polymer.
The fluorine-containing antifouling agent preferably further has a substituent that contributes to bond formation or compatibility in the hard coat layer film. These substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like.
The fluorine-containing antifouling agent may be a polymer or an oligomer with a compound containing no fluorine atom.

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

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

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

  a is preferably 1 to 1.75, more preferably 1 to 1.5, and if it is 1 or more, the synthesis of the compound is industrially easy, and if it is 1.75 or less, curability and antifouling properties are obtained. Coexistence is easy.

The polymerizable unsaturated group in R ^A, include the same polymerizable unsaturated group and R _A in formula (F), in preferably (meth) acryloyl group, (meth) acryloyloxy group, and these groups A group in which an arbitrary hydrogen atom is substituted with a fluorine atom.

When the fluorine-containing compound contains a siloxane structure, a preferred example of the siloxane structure is a structure having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include (meth) acryloyl group, (methacryloyloxy) group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group Examples thereof include a group containing a group and the like, and a (meth) acryloyloxy group is particularly preferable from the viewpoint of suppressing bleeding out of the antifouling agent. As the number of ^{substituents, 1500g · mol -1 ~20000g · mol} -1 as a functional group equivalent is preferred from the viewpoint of uneven distribution improvement and bleed out suppression of antifouling agents.

R ^f is an organic group containing a fluorine atom, and is a group represented by C _x F _{2x + 1} (CH ₂ ) _p — (wherein x is an integer of 1 to 8, and p is an integer of 2 to 10). Or it is preferably a perfluoropolyether-substituted alkyl group. b is preferably 0.2 to 0.4, more preferably 0.2 to 0.25. When 0.2 or more, antifouling property is improved, and when 0.4 or less, curability is improved. To do. R ^f is preferably a C 8 perfluoroalkyl group.

R ^A is an organic group containing a (meth) acryl group, and the bond to the Si atom is more preferably a Si—O—C bond from the viewpoint of easy industrial synthesis. c is preferably 0.4 to 0.8, more preferably 0.6 to 0.8. When 0.4 or more, curability is improved, and when 0.8 or less, antifouling property is improved. To do.

  Further, a + b + c is preferably 2 to 2.7, more preferably 2 to 2.5. If it is less than 2, uneven distribution to the surface hardly occurs, and if it is more than 2.7, it is hardenable and antifouling. It becomes impossible to balance.

  When the fluorine-containing compound contains a siloxane structure, the fluorine-containing compound has 3 or more F atoms and 3 or more Si atoms, preferably 3 to 17 F atoms and 3 Si atoms in one molecule. It is preferable to contain ~ 8 pieces. When there are 3 or more F atoms, the antifouling property is sufficient, and when there are 3 or more Si atoms, uneven distribution on the surface is promoted 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 described in JP-A-2007-14584.

  When the fluorine-containing compound contains a siloxane structure, the siloxane structure may be any of linear, branched, and cyclic, and among these, compounds having a branched or cyclic structure are particularly described below. It is preferable because it is compatible with a compound having a double bond, has no repelling, and tends to be unevenly distributed on the surface.

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

In addition, the compound having a cyclic structure of siloxane structure is preferably a compound represented by the following formula (F-8).
Formula (F-8):
(R ^f RSiO) (R ^A RSiO) _n (wherein R, R ^f , and R ^A are the same as described above, and n ≧ 2, particularly 3 ≦ n ≦ 5)

  The following compounds etc. are mentioned as a specific example of such a fluorine-containing polysiloxane compound.

The weight average molecular weight (Mw) of the fluorine-containing antifouling agent can be measured using molecular exclusion chromatography such as 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 still more preferably 1000 or more and less than 3500. It is preferable that Mw is 400 or more because the surface migration property of the antifouling agent becomes high. Further, if the Mw is less than 5000, the surface migration of the fluorine-containing antifouling agent is not hindered during the process of curing from coating, and it is easy to orient uniformly on the hard coat layer surface. This is preferable because the hardness is improved.
However, when the fluorine-containing compound contains a siloxane structure, Mw is less than 15000, preferably 1000 or more and less than 5000, and more preferably 1000 or more and less than 3500.

  The addition amount of the fluorine-containing antifouling agent is preferably 1% by mass to 20% by mass, and preferably 1% by mass to 15% by mass with respect to the total solid content in the hard coat layer or the hard coat layer forming composition. More preferably, 1% by mass to 10% by mass is even more preferable. When the addition amount of the fluorine-containing antifouling agent is 1% by mass or more with respect to the total solid content in the hard coat layer or the hard coat layer forming composition, the ratio of the antifouling agent having water and oil repellency is moderate. Thus, sufficient antifouling property can be obtained. Further, when the addition amount of the fluorine-containing antifouling agent is 20% by mass or less based on the total solid content in the hard coat layer or the hard coat layer forming composition, an antifouling agent that cannot be mixed with the resin component is deposited on the surface. And the film is not whitened or white powder is not generated on the surface.

  Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-containing antifouling agent, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30 mass%-70 mass%, It is 40 mass%-70 mass%. Most preferably it is.

  Examples of preferred fluorine-containing antifouling agents are Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833, Optool DAC (trade name), DIC Corporation, MegaFac (registered) Trademarks) F-171, F-172, F-179A, defender MCF-300, MCF-323 (trade name) and the like are included, but not limited thereto.

[Polysiloxane compound having a polymerizable unsaturated group and a weight average molecular weight of 15000 or more]
Next, a polysiloxane compound having a polymerizable unsaturated group and having a weight average molecular weight of 15000 or more that can be used as the component g) will be described. Hereinafter, a polysiloxane compound having a molecular weight of 15000 or more is referred to as a “polysiloxane antifouling agent”.

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

Preferable examples of the polysiloxane antifouling agent include compounds having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units.
The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include (meth) acryloyl group, (methacryloyloxy) group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group Examples thereof include a group containing a group and the like, and a (meth) acryloyloxy group is particularly preferable from the viewpoint of suppressing bleeding out of the antifouling agent. Further, the number of substituents is preferably 1500 to 20000 g · mol ⁻¹ as a functional group equivalent from the viewpoint of improving the uneven distribution of the antifouling agent and suppressing bleeding out.

  The polysiloxane antifouling agent is a compound containing 3 or more F atoms and 3 or more Si atoms, preferably 3 to 17 F atoms and 3 to 8 Si atoms in one molecule. Is preferred. When there are 3 or more F atoms, the antifouling property is sufficient, and when there are 3 or more Si atoms, uneven distribution on the surface is promoted and the antifouling property is sufficient.

The polysiloxane antifouling agent can be produced using a known method described in JP-A-2007-14584.
Examples of the additive having a polysiloxane structure include a reactive group-containing polysiloxane {for example, “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), "AK-5", "AK-30", "AK-32" (trade name), manufactured by Toa Gosei Co., Ltd .; "Silaplane FM0725", "Silaplane FM0721" (Trade name), manufactured by Chisso Corp .; “DMS-U22”, “RMS-033”, “UMS-182” (trade name), manufactured by Gelest, etc.} are also preferably added. Moreover, the silicone type compound of Table 2 or Table 3 of Unexamined-Japanese-Patent No. 2003-112383 can also be used preferably.

  The siloxane structure contained in the polysiloxane antifouling agent may be any of linear, branched, and cyclic. Among them, a compound having a branched or cyclic structure is an unsaturated double bond described later. It is preferable because it has good compatibility with a compound having an alkenyl group, has no repelling, and tends to be unevenly distributed on the surface.

The weight average molecular weight of the polysiloxane antifouling agent is 15000 or more, preferably 15000 or more and 50000 or less, more preferably 18000 or more and 30000 or less. If the weight average molecular weight of the polysiloxane antifouling agent is less than 15,000, the surface uneven distribution of the polysiloxane is reduced, which is not preferable from the viewpoint of causing deterioration of the antifouling property and a decrease in hardness. However, the above problem does not occur when the fluorine-containing compound having a polymerizable unsaturated group has a polysiloxane structure.
The weight average molecular weight of the polysiloxane antifouling agent can be measured using molecular exclusion chromatography 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 with respect to the total solid content in the hard coat layer or the hard coat layer forming composition. Is more preferable, 1 mass% or more and less than 15 mass% is still more preferable, and 1 mass% or more and less than 10 mass% is the most preferable. When the addition amount of the polysiloxane antifouling agent is 1% by mass or more with respect to the total solid content in the hard coat layer or the hard coat layer forming composition, the ratio of the antifouling agent having water and oil repellency is moderate. Thus, sufficient antifouling property can be obtained. Moreover, when 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, an antifouling agent that cannot be mixed with the resin component is deposited on the surface. And the film is not whitened or white powder is not generated on the surface.

The distribution of the antifouling agent in the film thickness direction in the hard coat layer is 51 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. % <X / Y <100% is preferably satisfied. When X / Y is greater than 51%, the antifouling agent is not distributed to the inside of the hard coat layer, which is preferable in terms of antifouling properties and film hardness. The vicinity of the surface refers to a region having a depth of less than 1 μm from the surface of the hard coat layer, and is an F ⁻ fragment or Si ₂ C ₅ H ₁₅ O ⁺ measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS). It can be measured by the ratio of fragments.

g) The antifouling agent is preferably an antifouling agent that dissolves in a liquid or solvent at 20 ° C. The solvent can be appropriately selected according to the polarity of the compound, but is preferably an organic solvent miscible with dimethyl carbonate, and examples thereof include aliphatic or reporting alcohols, ketones, esters, and ether solvents. It is particularly preferred if it is dissolved in dimethyl carbonate.
g) From the viewpoint of antifouling properties, the surface tension of the antifouling agent is preferably 25.0 mN / m or less, more preferably 23.0 mN / m or less, and 16.0 mN / m. More preferably, it is as follows.
The surface tension of the antifouling agent is the surface tension of a single film and can be measured as follows.

(Measurement method of surface tension of antifouling agent)
An antifouling agent was spin-coated on a quartz substrate, and when it contained a solvent, it was dried to produce a film. Subsequently, using a contact angle meter [“CA-X” type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.], using a pure water as a liquid in a dry state (20 ° C./65% RH), a diameter of 1 A droplet of 0.0 mm was formed on the needle tip, and this was brought into contact with the surface of the spin coat film to form a droplet on the film. The angle formed between the tangent to the liquid surface and the film surface at the point where the film and the liquid are in contact with each other, and the angle on the side containing the liquid was defined as the contact angle. Further, the contact angle was measured using methylene iodide instead of water, and the surface free energy was obtained from the following equation.
What is surface free energy (γs ^v : unit, mN / m)? K. Owens: J.M. Appl. Polym. Sci. , 13, 1741 (1969), from the contact angles θ _H2O and θ _{CH2I2 of} pure water H ₂ O and methylene iodide CH ₂ I ₂ experimentally determined on the antireflection film, the following simultaneous equations a , B, and defined by a value γs ^v (= γs ^d + γs ^h ) represented by the sum of γs ^d and γs ^h .
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 _{H 2 O} ^d = 21.8, γ _{H 2 O} ^h = 51.0, γ _{H 2 O} ^v = 72.8,
γ _CH2I2 ^d = 49.5, _γCH2I2 ^h = 1.3, _γCH2I2 ^v = 50.8

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

(solvent)
The composition for forming a hard coat layer may contain a solvent. The solvent is selected from the viewpoints of being able to dissolve or disperse each component, easily forming a uniform surface in the coating process and the drying process, ensuring liquid storage stability, and having an appropriate saturated vapor pressure. Various solvents can be used.
The solvent can be used by mixing two or more kinds of solvents. In particular, from the viewpoint of drying load, it is preferable that the main component is a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature, and a small amount of solvent having a boiling point of more than 100 ° C. is included for adjusting the drying speed.
In the composition for forming a hard coat layer, the solvent having a boiling point of 80 ° C. or less is preferably contained in an amount of 30% by mass to 80% by mass, and further 50% by mass to 70% by mass in the total solvent of the coating composition. preferable. By setting the solvent ratio with a boiling point of 80 ° C. or less to the above ratio, the penetration of the resin component into the polyester film is moderately suppressed, and the rate of increase in viscosity due to drying is increased, so that particle sedimentation can be suppressed.

The solvent whose boiling point is 100 degrees C or less is mentioned below. The temperature indicated is the boiling point of each solvent.
Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), dichloromethane, and the like. (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), halogenated hydrocarbons such as trichlorethylene (87.2 ° C) , Ethers such as diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), tetrahydrofuran (66 ° C), ethyl formate (54.2 ° C), acetic acid Esters such as methyl (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl ketone: , Ketones such as MEK, which may be referred to as MEK, methanol (64.5 ° C.), ethanol (78.3 ° C.), 2-propanol (82.4 ° C.), 1-propanol (97. Alcohols such as 2 ° C), cyano compounds such as acetonitrile (81.6 ° C), propionitrile (97.4 ° C), carbon disulfide (46.2 ° C), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point exceeding 100 ° C. include octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), chlorobenzene (131.7 ° C.), Dioxane (101.3 ° C.), dibutyl ether (142.4 ° C.), isobutyl acetate (118 ° C.), cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone (methyl isobutyl ketone, hereinafter referred to as MIBK) 115.9 ° C., 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

(Surfactant)
In the hard coat layer or the hard coat layer forming composition, it is also preferable to use various surfactants, wind unevenness inhibitors and the like (hereinafter also referred to as surfactants collectively). In general, by containing a surfactant or a wind non-uniformity inhibitor, it is possible to suppress film thickness non-uniformity or the like due to drying variation due to local distribution of dry wind.

  Specifically, the surfactant preferably contains at least one of a fluorine-based surfactant and a silicone-based surfactant. The surfactant is preferably an oligomer or a polymer rather than a low molecular compound.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (hereinafter sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following (i): An acrylic resin, a methacrylic resin, and a copolymerizable copolymer containing a repeating unit corresponding to the monomer, or a repeating unit corresponding to the monomer (i) and a repeating unit corresponding to the monomer (ii) below. Copolymers with vinyl monomers are useful.

(I) Fluoroaliphatic group-containing monomer represented by the following formula (i-1) Formula (i-1)

In the 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 is an integer of 1 to 6, and n is 2 to 4 Represents an 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, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(Ii) Monomer represented by the following formula (ii-1) copolymerizable with the above (i): Formula (ii-1)

In the 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 having 1 to 4 carbon atoms. Group, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - are preferred.
R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent for the alkyl group of R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group, and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

  The amount of the fluoroaliphatic group-containing monomer represented by the formula (i-1) used for the fluoropolymer is 10 mol% or more based on each monomer of the fluoropolymer, preferably 15 mol. % To 70 mol%, more preferably in the range of 20 mol% to 60 mol%.

  The preferred weight average molecular weight of the fluoropolymer is preferably 3000 to 100,000, more preferably 5,000 to 80,000. Furthermore, the preferable addition amount of a fluorine-type polymer is the range of 0.001 mass part-5 mass parts with respect to 100 mass parts of coating liquid, More preferably, it is the range of 0.005 mass part-3 mass parts, More preferably, it is the range of 0.01 mass part-1 mass part. If the addition amount of the fluorine-based polymer is 0.001 part by mass or more, the effect of adding the fluorine-based polymer is sufficiently obtained. If the addition amount is 5 parts by mass or less, the coating film cannot be sufficiently dried, There is no problem of adversely affecting the performance as a film.

Examples of preferable silicone compounds include X-22-174DX, X-22-2426, X22-164C, X-22-176D (trade names) manufactured by Shin-Etsu Chemical Co., Ltd .; manufactured by Chisso Corporation. FM-7725, FM-5521, FM-6621 (trade name); DMS-U22 manufactured by Gelest, RMS-033 (trade name); SH200, DC11PA, ST80PA, L7604 manufactured by Toray Dow Corning Co., Ltd. , FZ-2105, L-7604, Y-7006, SS-2801 (trade name); “TSF400 (trade name)” manufactured by Momentive Performance Materials Japan, but not limited thereto.
The silicone-based surfactant is preferably contained in an amount of 0.01% by mass to 0.5% by mass when the total solid content of the hard coat layer forming composition is 100% by mass. -0.3 mass% is more preferable.

(Matte particles)
The hard coat layer or the hard coat layer forming composition has matte particles having an average particle diameter 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 surface irregularities. It may contain. Moreover, in order to adjust the viscosity of a coating liquid, a high molecular compound, an inorganic layered compound, etc. can also be included. e) may be used as matte particles.

[Method of applying 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 adjusted composition for forming a hard coat layer is applied onto a base film, heated and dried. The drying method will be described later.
Examples of the method for applying the composition on the support include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, micro gravure coating, and die coating. . Among these, a micro gravure coating method, a wire bar coating method, and a die coating method are preferable, and a die coating method is more preferable. Details of the die coating method are described in detail, for example, in US Pat. No. 2,681,294 and JP-A-2006-122889, and these descriptions can be referred to.

The composition for forming a hard coat layer is applied on a substrate film and then dried to remove the solvent contained in the composition, and the composition for forming a hard coat layer is cured to form a hard coat layer. Drying can be carried out, for example, by transporting the base film on which the hard coat layer forming composition layer is formed and passing it through a heated zone.
The temperature in the drying zone used for drying is preferably 25 ° C to 140 ° C. The temperature in the drying zone does not necessarily have to be uniform, the first half of the drying zone is relatively low temperature, for example, in the range of 25 ° C to 100 ° C, and the latter half is relatively high temperature, eg, 60 ° C to 140 ° C. A range is preferable.
However, the temperature in the drying zone is equal to or lower than the temperature at which components other than the solvent contained in the hard coat layer forming composition layer and the hard coat layer forming composition layer formed on the support are volatilized. It is preferable that More specifically, for example, a commercially available photo radical generator used in combination with an ultraviolet curable resin includes a compound in which about several tens of percent volatilizes within a few minutes in 120 ° C. warm air. Among functional acrylate monomers, bifunctional acrylate monomers, etc., there are compounds whose volatilization proceeds in hot air at 100 ° C. In the case where a compound that easily volatilizes at a heating temperature of around 100 ° C. is used for the composition for forming a hard coat layer, the temperature in the heating zone is equal to or higher than the volatilization temperature of the solvent, and components other than the solvent are volatilized. It is preferable that the temperature is not higher than the starting temperature.

When the composition for forming the hard coat layer is applied on the base film and then dried by blowing dry air on the composition layer for forming the hard coat layer, the solid content concentration of the composition for forming the hard coat layer is 1% by mass. When it is ˜50 mass%, the wind speed on the coating film surface of the hard coat layer forming composition is in the range of 0.1 m / second to 2 m / second, so that the drying unevenness of the hard coat layer forming composition layer is It is preferable to prevent this.
In addition, as another preferable example of the drying condition, after the hard coat layer forming composition layer is applied on the base film, the surface opposite to the surface on which the base film composition is applied in the drying zone. The method of adjusting the temperature difference of the temperature of the conveyance roll which contacts and the temperature of a base film within 0 to 20 degreeC is mentioned. By making the temperature difference of a conveyance roll and a base film into the said range, since the drying nonuniformity of the hard-coat layer resulting from the heat transfer nonuniformity on a conveyance roll can be prevented, it is preferable.

In the drying zone, 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 a curing zone for curing the hard coat layer by ionizing radiation irradiation. The coat layer can be cured.
When the composition for forming a hard coat layer is an ultraviolet curable composition, the curing zone is preferably a zone for irradiating an ultraviolet lamp. The irradiation dose of the ultraviolet lamp is ^preferably in the range of ^{10mJ / cm 2 ~1000mJ / cm 2} . The hard coat layer is suitably cured by irradiating the ultraviolet ray with the above-mentioned irradiation amount. When performing ultraviolet irradiation, the irradiation dose distribution in the width direction of the hard coat layer forming composition layer on the support transported in the curing zone on the support is up to both ends with respect to the central maximum UV irradiation dose. The distribution is preferably 50% to 100%, and more preferably 80% to 100%.
Purging with an inert gas such as nitrogen gas in the curing zone to lower the oxygen concentration for the purpose of suppressing the inhibition of curing by oxygen in the ultraviolet curable composition and further promoting the surface curing of the hard coat layer. it can. When reducing the oxygen concentration, the oxygen concentration is preferably 0.01% to 5%, and the distribution in the width direction of the oxygen concentration in the curing zone 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 promoting the curing reaction, the temperature in the curing zone is preferably 25 ° C to 100 ° C, more preferably 30 ° C to 80 ° C, and even more preferably 40 ° C to 70 ° C.

  When forming a hard-coat layer, another functional layer can be provided as needed. When other functional layers are stacked in addition to the hard coat layer at the time of forming the hard coat layer, a multilayer coating for simultaneously applying a plurality of layers may be performed, or a sequential coating for sequentially forming may be performed. The formation of other functional layers that are arbitrarily formed can be performed in accordance with the above-described method for producing a hard coat layer. Examples of other functional layers that can be provided when the hard coat layer is formed include an easy-adhesion layer, a refractive index adjustment layer, and an ultraviolet absorption layer.

[Decoration layer]
The decorative film of the present disclosure has a decorative layer. A decoration layer has a decoration layer in at least one part with respect to the whole area | region in planar view of a decoration film.
A decoration layer may be provided in the whole surface of a base material, and may be provided in a part.
The decorative layer imparts various design properties to the decorative film.
As the decorative layer, for example, there are characters and figures visually recognized around the image display unit when used as an image display panel, or a black bordered decorative layer provided on the image display unit in a frame shape, etc. Can be mentioned.
FIG. 3 is a plan view illustrating an aspect of the decorative film 10 of the present disclosure.
Especially, it is preferable that the decoration layer 14 of the decoration film 10 is provided in the peripheral edge part in planar view of the decoration film 10 in an image display part, as shown in FIG. That is, on the back side of the substrate containing a transparent polyester film, that is, on the member side to which the decorative film is attached, the peripheral edge portion is provided as a black frame-shaped light-shielding layer, concealing internal wiring, etc. The aspect which improves is preferable.

A decoration layer is formed as a resin layer containing the coloring agent according to the objective. The colorant contained in the decorative layer can be appropriately selected from various colorants according to the purpose of use. In general, when the decorative layer is used as a light-shielding layer, a light-shielding colorant 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. Is used.
Examples of the black pigment contained in the decorative layer include carbon black, titanium black, and the like, both of which have good light shielding properties and are preferable when used as a light shielding layer. Examples of white pigments include titanium oxide and zinc oxide.

  The decorative layer may be provided by applying a composition for forming a decorative layer containing a colorant and a binder resin in a pattern, for example, a hard coat layer or a surface of a substrate containing a polyester film by a printing method. Alternatively, it may be provided by a transfer method. Moreover, you may provide by forming the composition for positive type or negative type decoration layer formation on the surface of the base material containing a hard-coat layer or a polyester film, and patterning. As a composition for positive type decoration layer formation, the composition containing the compound which improves the solubility of binder resin, such as a coloring agent, binder resin, and a photo-acid generator, is mentioned. Examples of the negative decorative layer forming composition 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.
Examples of the material for forming the decoration layer include printing ink containing a colorant that can be used on a resin substrate to form a colored film.
From the viewpoint of simplicity, it is also a preferred embodiment that the decorative layer is formed by a printing method using a printing ink containing the aforementioned colorant.
Examples of the printing method include a silk printing method, a screen printing method, an ink jet printing method, a gravure printing method, and a thermal transfer printing method. Of these, the silk printing method, the screen printing method, and the thermal transfer printing method are preferable from the viewpoint of printing a decorative layer with good concealability. According to the printing method, the decorative layer can be easily provided in a pattern on the entire surface or a desired region.

As a printing ink used for forming a decorative layer by a silk 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 is used. In particular, solvent-based inks are preferably used because they only need to dry the solvent in a drying furnace, and therefore can be printed at low cost because no device such as a UV irradiation device is required.
As the ink used for the thermal transfer system, a resin type or a wax type is used. Of these, the resin type is preferably used because of its excellent weather resistance.

  In addition, the above-described positive or negative decorative layer-forming composition capable of forming a pattern is applied to at least one surface of a substrate including a polyester film by a coating method, a transfer method, or the like. A patterned decorative layer can also be formed by pattern exposure and development in which a forming composition layer is formed and exposed through a mask. According to the 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 in the above-described range, it is difficult for color loss and printing failure to occur, and it becomes easy to obtain suitable design properties.

Although the example of the preferable layer structure of the decorating film of this indication is shown below, it is not limited to these layer structures. The following layer structure is described in order from the member side on which the decorative film is provided.
・ Decoration layer / Base material including polyester film / Hard coat layer ・ Base material including polyester film / Hard coat layer / Decoration layer ・ Base material including polyester film / Decoration layer / Hard coat layer From the viewpoint of scratch resistance, the decorative layer is disposed on one surface of the polyester film, and the hard coat layer is disposed on the surface opposite to the surface on which the decorative layer of the polyester film is disposed. It is preferable.
That is, it is preferable to have a decoration layer in the vicinity of a member on which the decorative film of the present disclosure is provided, 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 region of the decorative layer 14 in the decorative film 10. In FIG. 3, the decorative layer 14 is provided on the peripheral edge of the decorative film 10. In the non-formation area | region of the decoration layer 14, a polyester film and a hard-coat layer can be visually recognized by planar view.

FIG. 4A, FIG. 4B, and FIG. 4C are schematic side views showing a modified example of a laminated structure of a base material / hard coat layer including a decorative layer / polyester film. The decorative film 10 shown in FIG. 4A has a decorative layer 14, a base material 16 including a polyester film, and a hard coat layer 18 in this order from the member side where the decorative film 10 is arranged, that is, from the lower side of FIG. 4A. It has a laminated aspect. The decorative film 20 shown in FIG. 4B has an aspect in which the base material 16 including the polyester film, the hard coat layer 18 and the decorative layer 14 are laminated in this order from the member side on which the decorative film 20 is disposed. The decorative film 22 shown in FIG. 4C has a mode in which the base material 16 including the polyester film, the decorative layer 14, and the hard coat layer 18 are laminated in this order from the member side on which the decorative film 22 is disposed.
The decorative film of the present disclosure may have any of the laminated structures described above. The decorative film may have an optional layer 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 modified example of the schematic cross-sectional view taken along the line AA of the decorative film 10 shown in FIG. 4A.
The decorative film 22 shown in FIG. 4A has a laminated structure similar to that of the side view shown in FIG. 4C. The decorative film 22 includes a base material 16 including a polyester film on the side where the decorative film is disposed, and includes a polyester film. 3 has a decorative layer 14 having a pattern shape as shown in FIG. 3 in a plan view on one peripheral edge of the surface of the material 16, and a hard coat is provided on the side including the decorative layer 14 of the base material 16 including a polyester film. It has a layer 18.
In the decorative film 10 shown in FIG. 5B, as shown in FIG. 3 in a plan view on the peripheral portion of the surface on the member side where the decorative film 10 is disposed, which is one surface of the base material 16 including the polyester film. It has a decorative pattern 14 in the shape of a pattern. The hard coat layer 18 is provided on the surface opposite to the surface having the decorative layer 14 of the substrate 16 including the polyester film.
In addition, the layer structure of a decoration layer is not limited to the above-mentioned example, A various modified example can be taken.

  The decorative film of the present disclosure may include other layers (arbitrary layers) in addition to the polyester film, the decorative layer, and the hard coat layer described above. Examples of the optional layer include an easy adhesion layer, an antireflection layer (a laminated film of one or more high refractive index layers and one or more low refractive index layers), a refractive index adjusting layer such as an antiglare layer and a low refractive index layer. Examples thereof include, but are not limited to, an antistatic layer and an ultraviolet absorbing layer. For an arbitrary layer, for example, the description in paragraphs 0069 to 0091 of Japanese Patent No. 5048304 can be referred to.

(Low refractive index layer)
The decorative film of this indication can also form a low-refractive-index layer on a hard-coat layer for the purpose of provision of a reflectance reduction effect. The low refractive index layer is a layer having a lower refractive index than the hard coat layer. When the low refractive index layer is provided on the surface of the hard coat layer, the thickness of the low refractive index layer is preferably 50 nm to 200 nm, more preferably 70 nm to 150 nm, and further preferably 80 nm to 120 nm. preferable.

The refractive index of the low refractive index layer is preferably lower than the refractive index of the layer immediately below. The refractive index of the low refractive index layer is preferably 1.20 to 1.55, more preferably 1.25 to 1.46, and even more preferably 1.30 to 1.40.
When the low refractive index layer is provided, the thickness of the low refractive index layer is preferably 50 nm to 200 nm, and more preferably 70 nm to 100 nm.
The low refractive index layer is preferably obtained by curing a curable composition for forming the low refractive index layer.
As an aspect of a preferable curable composition for forming a low refractive index layer,
(1) A composition containing a fluorine-containing compound having a crosslinkable functional group or a polymerizable functional group,
(2) a composition comprising as a main component a hydrolysis-condensation product of a fluorine-containing organosilane material;
(3) A composition containing a monomer having two or more ethylenically unsaturated groups and inorganic particles (in particular, inorganic particles having a hollow structure are preferred), wherein the inorganic particles include inorganic particles having a hollow structure. Is preferred. )
Etc.
Each of the compositions for forming a low refractive index layer of the above (1) and (2) also preferably contains inorganic particles, and the inorganic particles have a hollow structure having a lower refractive index than the solid inorganic particles as the inorganic particles. Is particularly preferred from the standpoint of lowering the refractive index or adjusting the amount of inorganic particles added and the refractive index.

(1) Composition containing a fluorine-containing compound having a crosslinkable or polymerizable functional group As the fluorine-containing compound having a crosslinkable or polymerizable functional group, a fluorine-containing monomer and a crosslinkable or polymerizable functional group are used. Mention may be made of a fluorine-containing polymer which is a copolymer with the monomer it has. Specific examples of these fluoropolymers are described in JP2003-222702A, JP2003-183322A, and the like.

  Moreover, when using said fluorine-containing polymer for formation of a low refractive index layer, as described in Unexamined-Japanese-Patent No. 2000-17028, you may use together the hardening | curing agent which has a polymerizable unsaturated group suitably. Further, as described in JP-A-2002-145952, the combined use of a fluorine-containing polymer and a compound having a fluorine-containing polyfunctional polymerizable unsaturated group is also preferred. Examples of the compound having a polyfunctional polymerizable unsaturated group include monomers having two or more ethylenically unsaturated groups described as the curable resin for the low refractive index layer. In addition, as a compound used for forming the low refractive index layer, an organolane hydrolysis condensate described in JP-A No. 2004-170901 is also preferable, and in particular, an organosilane hydrolysis condensate containing a (meth) acryloyl group. Is preferred. These compounds are particularly preferred because they have a large combined effect for improving scratch resistance, particularly when a compound having a polymerizable unsaturated group is used in the polymer body.

When the polymer itself does not have sufficient curability, the curability necessary for the composition for forming a low refractive index layer can be imparted by blending a crosslinkable compound.
For example, when the polymer main body contains a hydroxyl group, various amino compounds are preferably used as the curing agent. Examples of the amino compound used as the crosslinkable compound include compounds containing a total of two or more of either one or both of a hydroxyalkylamino group and an alkoxyalkylamino group. Specific examples of the amino compound used as the crosslinkable compound include melamine compounds, urea compounds, benzoguanamine compounds, glycoluril compounds, and the like. For curing these compounds, an organic acid or a salt thereof is preferably used.

(2) Composition mainly composed of hydrolyzed condensate of fluorine-containing organosilane material The composition mainly composed of hydrolyzed condensate of fluorine-containing organosilane compound also has a low refractive index and the hardness of the coating surface. Is preferable. As the fluorine-containing organosilane material, a condensate of a compound containing a hydrolyzable silanol at one or both ends with respect to a fluorinated alkyl group and tetraalkoxysilane is preferable. Specific compositions are described in JP-A Nos. 2002-265866 and 317152.

(3) A composition comprising a monomer having two or more ethylenically unsaturated groups and inorganic particles having a hollow structure Further, as another preferred embodiment of the low refractive index layer, it contains particles having a low refractive index and a resin. And a low refractive index layer. The low refractive index particles contained in the low refractive index layer may be organic particles or inorganic particles, but hollow particles having pores inside are preferable. Specific examples of the hollow particles include silica-based particles described in JP-A No. 2002-79616.
The refractive index of the particles used for the low refractive index layer is preferably 1.15 to 1.40, more preferably 1.20 to 1.30.
Examples of the resin used for the low refractive index layer include a resin derived from a monomer having two or more ethylenically unsaturated groups described in the item of the antiglare layer.

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

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

  For the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties, etc. to the low refractive index layer, known polysiloxane antifouling agents, fluorine antifouling agents, slipping agents, etc. It can be added as appropriate.

  As an additive having a polysiloxane structure, a reactive group-containing polysiloxane {for example, 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), manufactured by Shin-Etsu Chemical Co., Ltd .; AK-5, AK-30, AK- 32 (product name), manufactured by Toa Gosei Co., Ltd .; “Silaplane FM0725”, “Silaplane FM0721” (product name), manufactured by JNC Co., Ltd., etc.} are also preferably added. Moreover, the silicone type compound of Table 2 and Table 3 of Unexamined-Japanese-Patent No. 2003-112383 can also be used preferably.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, 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.), alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl, etc. Group or an alkyl group substituted with these, and may have an ether bond (for example, CH ₂ OCH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH ₂ CH _{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 film. The fluorine-based compound preferably has a plurality of the above substituents. When the fluorine-based compound has a plurality of the above substituents, they may be the same or different from each other. Preferable examples of the substituent include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like.
There is no restriction | limiting in particular in the molecular weight of a fluorine compound. The fluorine-based compound may be a polymer having a partial structure not containing a fluorine atom, or may be an oligomer.
Although there is no restriction | limiting in particular in fluorine atom content in a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30 mass%-70 mass%, It is 40 mass%-70 mass% Is most preferred.
Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833, OPTOOL DAC (above trade name), DIC Corporation, MegaFac (registered trademark). Examples include, but are not limited to, F-171, F-172, F-179A, defender MCF-300, MCF-323 (trade name) and the like.
These polysiloxane fluorine-based compounds or compounds having a polysiloxane structure are preferably added in the range of 0.1% by mass to 10% by mass of the total solid content of the low refractive index layer, particularly preferably 1% by mass to 5%. This is a case of mass%.

[Uses of decorative film]
The use of the decorative film according to the present disclosure is not particularly limited, and can be suitably used without particular limitation as long as it is a use that requires scratch resistance and is required to give a design. In particular, in applications that require punching or the like for attachment to the member, for example, for image display devices, touch panels, etc., peeling of the decorative layer, cracking, cracking during processing is suppressed, It can be said that the effect is remarkable.

[Method for producing decorative film]
The method for producing a decorative film according to the present disclosure uses a tenter-type stretching device including a plurality of clips that respectively travel along a pair of rails installed on both sides of a film conveyance path, and uses an unstretched polyester film as a clip. In the gripped state, a transverse stretching process that stretches in a direction perpendicular to the film conveyance path, a heat setting process that heat-fixes the polyester film after transverse stretching, and a heat-fixing process that heats the polyester film after the heat-fixing process. And a heat relaxation step of narrowing the length of the polyester film in the direction perpendicular to the film conveyance direction and the film conveyance direction, and in the heat relaxation step, orthogonal to the film conveyance direction of the polyester film after the heat setting step The relaxation rate in the direction perpendicular to the film transport direction, which is the ratio of narrowing the length in the direction to be applied, is 0. 150% at a temperature of 150 ° C. in the direction perpendicular to the film conveyance direction and the film conveyance direction, with the relaxation rate in the film conveyance direction of the polyester film heat-fixed 0.1% to 7%. A polyester film forming step for forming a polyester film having a thermal shrinkage rate of 3.0% or less when giving a heat history for a minute, and forming a decorative layer on at least a part of one surface of the polyester film A decoration layer forming step, and a hard coat layer forming step of forming a hard coat layer on at least one surface of the polyester film.

A polyester film formation process is as having demonstrated in detail in the column of the polyester film, and its preferable aspect is also the same.
In the method for producing a decorative film, first, a polyester film as a substrate is formed. The order in which the hard coat forming process and the decorative layer forming process, which are subsequent processes, are performed is arbitrary, and can be appropriately selected and implemented according to the configuration of the decorative film.
Any of the hard coat layer forming step and the decorative layer forming step may be first, and in the case of forming the hard coat layer and the decorative layer on both surfaces of the base material including the polyester film, respectively. The hard coat layer and the decorative layer may be simultaneously formed by multilayer coating or simultaneous transfer method.

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

As the liquid crystal display device, a TN (Twisted Nematic) type, an STN (Super-Twisted Nematic) type, a TSTN (Triple Super Twisted Nematic) type, a multi-domain type, a VA (Vertical Alignment In) type, an IPS type, an IPS type OCB (Optically Compensated Bend) type etc. are mentioned.
The image display device is a liquid crystal display device including a liquid crystal cell and a polarizing plate according to 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. It is preferable. In this case, the image display element is a liquid crystal display element.

  In the image display device according to the present disclosure, the image display element is also preferably an organic electroluminescence display element.

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

There is no restriction | limiting in particular in the touchscreen which can apply the decorating film of this indication, According to the objective, it can select suitably. For example, a surface capacitive touch panel, a projected capacitive touch panel, a resistive touch panel, and the like can be given. Details will be described later as a resistive touch panel according to the present disclosure and a capacitive touch panel according to the present disclosure.
The touch panel includes so-called touch sensors and touch pads. The layer structure of the touch panel sensor electrode part in the touch panel is a bonding method in which two transparent electrodes are bonded, a method in which transparent electrodes are provided on both surfaces of a single substrate, a single-sided jumper or through-hole method, or a single-area layer method. Either is acceptable. In addition, the projected capacitive touch panel is preferably AC (alternating current) driving rather than DC (direct current) driving, and more preferably a driving method in which the voltage application time to the electrodes is short.

(Resistive touch panel)
The resistive film type touch panel according to the present disclosure is a resistive film type touch panel including a decorative film according to the present disclosure.
The resistive touch panel has a basic configuration in which conductive films of a pair of upper and lower substrates having a conductive film are disposed via a spacer at a position where the conductive films face each other. Note that the configuration of the resistive film type touch panel is known, and any known technique can be applied without any limitation in the present disclosure.

(Capacitive touch panel)
The capacitive touch panel according to the present disclosure is a capacitive touch panel including a decorative film according to the present disclosure.
Examples of the capacitive touch panel system include a surface capacitive type and a projected capacitive type. The projected capacitive touch panel has a basic arrangement in which an X-axis electrode (hereinafter also referred to as an X electrode) and a Y-axis electrode (hereinafter also referred to as a Y electrode) orthogonal to the X electrode are disposed via an insulator. Consists of configuration. As a specific aspect, an aspect in which the X electrode and the Y electrode are formed on separate surfaces on one substrate, an aspect in which the X electrode, the insulator layer, and the Y electrode are formed in this order on the single substrate. Examples include an embodiment in which an X electrode is formed on one substrate and a Y electrode is formed on another substrate (in this embodiment, a configuration in which two substrates are bonded together is the above basic configuration). The configuration of the capacitive touch panel is publicly known, and any known technology can be applied without any limitation in the present disclosure.

Hereinafter, the decorative film and the like of the present disclosure will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present disclosure is not construed as being limited by the specific examples shown below.
Unless otherwise specified, “parts” and “ppm” are based on mass.

[Example 1]
<Synthesis of raw material polyester>
(Raw material polyester 1)
As shown below, terephthalic acid and ethylene glycol are directly reacted to distill off water, esterify, and then, using a direct esterification method in which polycondensation is performed under reduced pressure, raw polyester 1 ( Sb catalyst system PET) was obtained.

(1) Esterification reaction In a first esterification reactor, 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol are mixed over 90 minutes to form a slurry, and continuously at a flow rate of 3800 kg / h. To the first esterification reactor. Further, an ethylene glycol solution of antimony trioxide was continuously supplied, and the reaction was carried out at a reaction vessel temperature of 250 ° C. with stirring and an average residence time of about 4.3 hours. In the reaction, antimony trioxide was continuously added in such an amount that the amount of Sb added was 150 ppm in terms of element.

  The obtained reaction product was transferred to a second esterification reaction vessel, and reacted with stirring at a temperature in the reaction vessel of 250 ° C. and an average residence time of 1.2 hours. The second esterification reactor is continuously supplied with an ethylene glycol solution of magnesium acetate and an ethylene glycol solution of trimethyl phosphate in such amounts that the added amount of Mg and the added amount of P are 65 ppm and 35 ppm in terms of element, respectively. did.

(2) a polycondensation reaction resulting esterification reaction product in the above was continuously supplied to the first polycondensation reaction vessel, stirred under a reaction temperature of 270 ° C., the reaction vessel pressure 20 torr (2.67 × 10 ^{- 3} MPa) and polycondensation with an average residence time of about 1.8 hours.

Further, the mixture was transferred to the second double condensation reaction tank, and the residence time was about 1 at a reaction tank temperature of 276 ° C. and a reaction tank pressure of 5 torr (6.67 × 10 ⁻⁴ MPa) with stirring in the second double condensation reaction tank. The reaction (polycondensation) was carried out for 2 hours.

Subsequently, it was further transferred to the third triple condensation reaction tank. In the third triple condensation reaction tank, the reaction tank temperature was 278 ° C., the reaction tank pressure was 1.5 torr (2.0 × 10 ⁻⁴ MPa), and the residence time was 1 Reaction (polycondensation) was carried out for 5 hours to obtain a reaction product (polyethylene terephthalate; PET).

  Next, the obtained reaction product was discharged into cold water in the form of a strand and immediately cut to prepare a polyester pellet “cross section: major axis: about 4 mm, minor axis: about 2 mm, length: about 3 mm”.

  The obtained polyester had IV = 0.63. The obtained polyester was designated as raw material polyester 1.

<Manufacture of polyester film>
-Film forming process-
After the raw material polyester 1 was dried to a water content of 20 ppm or less, it was put into a hopper 1 of a uniaxial kneading extruder 1 having a diameter of 50 mm. The raw material polyester 1 was melted at 300 ° C. and extruded from a die through a gear pump and a filter (pore diameter: 20 μm) under the following extrusion conditions.
The molten resin was extruded from the die under the conditions that the pressure fluctuation was 1% and the temperature distribution of the molten resin was 2%. Specifically, the back pressure was increased by 1% with respect to the average pressure in the barrel of the extruder, and the piping temperature of the extruder was heated at a temperature 2% higher than the average temperature in the barrel of the extruder.
The molten resin extruded from the die was extruded onto a cooling cast drum set at a temperature of 25 ° C., and adhered to the cooling cast drum using an electrostatic application method. It peeled using the peeling roll arrange | positioned facing the cooling cast drum, and the unstretched polyester film 1 was obtained.

-Formation of an easy adhesion layer-
The following compounds were mixed at the following ratio to prepare a coating liquid H1 for forming an easy adhesion layer.

(Coating liquid H1 for easy adhesion layer formation)
Polyester resin: (IC) 60 parts by mass Acrylic resin: (II) 25 parts by mass Melamine compound: (VIB) 10 parts by mass Particles: (VII) 5 parts by mass Details of the compounds used for forming the easy adhesion layer are shown below. .

-Polyester resin: (IC)-
A sulfonic acid aqueous dispersion of a polyester resin copolymerized with monomers having the following composition: Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene glycol / 1,4- Butanediol / diethylene glycol = 56/40/4 // 70/20/10 (mol%)

-Acrylic resin: (II)-
Aqueous dispersion of acrylic resin polymerized with monomers of the following composition Ethyl acrylate / n-butyl acrylate / methyl methacrylate / N-methylol acrylamide / acrylic acid = 65/21/10/2/2 (mass%) emulsion polymer ( Emulsifier: Anionic surfactant)

-Melamine compound: (VIB)-
Hexamethoxymethylmelamine-particles: (VII)-
Silica sol having an average particle size of 150 nm (the average particle size means the primary average particle size, that is, the average value of the primary particle size. The particle size is described in the table below).

-Application of easy adhesion layer to both sides of polyester film-
Using the wire bar while adjusting the coating liquid H1 for forming an easy-adhesion layer on one side of the unstretched polyester film 1 to an amount so that the coating film thickness after stretching is 50 nm by a bar coating method using a wire bar. Applied.

-Transverse stretching process-
The unstretched polyester film 1 was guided to a tenter (lateral stretching machine), and was stretched laterally by the following method and conditions while gripping the end of the film with a clip.

(Preheating part)
It heated with the hot air so that the surface temperature in the extending | stretching start point might be 89 degreeC.
In addition, the surface temperature at the stretching start point is a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, used at an emissivity of 0.95) at the center of the film width direction at the point of starting stretching. It was measured by.

(Extension part)
While preheated unstretched polyester film 1 was heated with hot air, it was stretched in the width direction (TD) using a tenter under the following conditions.
In addition, the surface temperature in each draw ratio time point is a radiation thermometer (used by Hayashi Denko, model number: RT61-2, emissivity 0.95) at the center of the film width direction at each draw ratio time point. It was measured by.

<Condition>
・ Horizontal stretch ratio: 4.1 times and surface temperature at the time of 2 times stretch: 90 ° C
-Surface temperature at the time of 3 times stretching: 94 ° C
-Surface temperature at the end of stretching: 95 ° C

(Heat setting process)
Subsequently, hot air from the up and down direction was applied to the film from the hot air blowing nozzle to the film, and heat setting was performed while controlling the surface temperature of the polyester film within the following range.
<Condition>
Maximum surface temperature (heat setting temperature): 168 ° C

(Thermal relaxation process)
In the hot talk method, relaxation by the tenter stretching device, relaxation for adjusting the transport speed and the clip interval during transport is performed by the means shown in Tables 1 to 4 below, and the relaxation rates shown in Tables 1 to 4 below. It was.
Relaxed transport tension in the thermal relaxation process, polyester film film surface temperature during thermal relaxation (described as “relaxed film surface temperature” in Tables 1 to 4), treatment time during thermal relaxation (in Tables 1 to 4) , Described as “relaxation treatment time”), cooling rate in the range of film surface temperature 70 ° C. ± 20 ° C. during cooling after thermal relaxation (described as “relaxation cooling rate” in Tables 1 to 4), They are shown in Tables 1 to 4, respectively.

(Cooling section)
Next, the film was cooled by applying cold air from above and below to the film from a cold air blowing nozzle. The film was cooled so that the surface temperature when the film was released from the tenter clip was 40 ° C.
In addition, the film surface temperature measured the position of the center part of a film width direction with the radiation thermometer (The product made from Hayashi Denko, model number: RT61-2, used by the emissivity 0.95).

(Recovery of film)
After cooling and releasing the film from the clip, both ends of the polyester film were trimmed by 20 cm. The film width after trimming was 2 m. Then, after extruding (knurling) with a width of 10 mm at both ends, a film having a length of 10,000 m was wound up in a roll form with a tension of 18 kg / m.
As described above, a polyester film 1 wound in the form of a roll and used for manufacturing the decorative film of Example 1 having a thickness of 150 μm was manufactured.

[Film measurement results]
About the obtained polyester film 1, the following physical property was measured. The measurement results are shown in Tables 1 to 4 below.

<Thickness>
The thickness of the obtained polyester film 1 was calculated | required as follows.
Using a contact-type film thickness meter (manufactured by Anritsu Co., Ltd.) for the polyester film of each example and comparative example, 50 points were sampled at equal intervals over 0.5 m in the longitudinally stretched direction (longitudinal direction). After sampling 50 points at equal intervals (50 equal parts in the width direction) over the entire width of the film in the film width direction (direction perpendicular to the longitudinal direction), the thicknesses of these 100 points were measured. The average thickness of these 100 points was determined and used as the thickness of the polyester film.

<Re, Rth, Re / Rth ratio>
Re and Rth were determined for the films obtained in each Example and Comparative Example by the method described above. From the obtained Re and Rth, the Re / Rth ratio was calculated.

<Heat shrinkage>
About a polyester film, about each of MD direction and TD direction, it cut | judged in width 30mm and length 120mm, the sample piece M of the polyester film was obtained, and two reference lines so that it might become an interval of 100 mm in a length direction beforehand Put.
The sample piece M was allowed to stand in a heating oven at 150 ° C. for 30 minutes under no tension, and then the sample piece M was cooled to room temperature, and the interval between the two reference lines was measured. The interval after the heat treatment to be measured is A [mm], and a numerical value [100 × (100−A) / 100] calculated from the interval 100 mm before the treatment and the interval Amm after the treatment [ %] Was defined as the thermal contraction rate of the sample piece M (150 ° C., 30 minutes).
In each direction, measurement was performed at three locations for each of three sample pieces in each direction, and an arithmetic average of a total of nine measurement results was used as a measurement value. The results are shown in Tables 1 to 4.

[Formation of hard coat layer]
A hard coat layer forming composition 1 having the following composition was prepared.
(Composition of hard coat layer forming composition 1)
・ 3,4-epoxycyclohexylmethyl acrylate [a) component]
40 parts by mass · DPHA: KAYARD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
[Component b] 55.4 parts by mass Irgacure 127: alkylphenone photopolymerization initiator (BASF (manufactured)) [c) component] 2.0 parts by mass Irgacure 290: sulfonium salt cationic polymerization initiator (manufactured by BASF (manufactured by BASF) )) [D) Component] 2.0 parts by mass FP-1: Fluorine compound having the following structure [anti-wind unevenness] 0.10 parts by mass Solvent: methyl ethyl ketone (MEK) 200 parts by mass Solvent: methyl isobutyl ketone ( MIBK) 100 parts by mass

The hard coat layer forming coating solution was applied by the following method.
The uniaxially stretched polyester film used in Example 1 wound up in a roll form was unwound and, as a post-process, the above-described coating liquid for forming a hard coat layer was applied by the following method.
A hard coat layer is provided with an easy-adhesion layer on one side of the film, and on the side where the easy-adhesion layer is formed, a die coating method using a slot die described in Example 1 of JP-A-2006-122889, with a conveyance speed of 30 m / min. Under the conditions, the coating liquid for forming a hard coat layer was applied, and dried in a drying zone at a temperature of 60 ° C. for 150 seconds. Then, it conveyed to the hardening zone and hardened the composition for hard-coat layer formation. In the curing zone, an oxygen concentration is about 0.1% under a nitrogen purge, and an irradiance of 400 mW / cm ² and an irradiation amount of 500 mJ / cm ² using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm. Was irradiated with UV rays to cure the hard coat layer, and the laminate having the hard coat layer formed on the film was wound up.
In addition, also in the other Example and the comparative example, the hard-coat layer was similarly formed using the base film of Tables 1-4. When the easy adhesion layer was not provided, a hard coat layer was formed on an arbitrary side of the film to be the base material.

<Film thickness of hard coat layer>
The film thickness of the hard coat layer was calculated by measuring the film thickness of the hard coat layer produced with a contact-type film thickness meter and subtracting the thickness of the polyester film measured in the same manner. The results are shown in Tables 1 to 4.

[Formation of decorative layer]
(1. Production of transfer film for decorative layer formation)
<Preparation of composition for decorating layer formation>
The decorative layer forming composition 1 (coloring composition) was obtained by the following procedure.
(Composition of composition 1 for decorating layer formation)
-K pigment dispersant (composition below) 137.4 parts by mass-Dipentaerythritol (penta / hexa) acrylate [Polymerizable compound] (Nippon Kayaku Co., Ltd., KAYARAD DPHA)
19.5 parts by mass, tricyclodecanediol dimethanol diacrylate [polymerizable compound] (Shin Nakamura Chemical Co., Ltd., A-DCP) 6.5 parts by mass, cyclohexyl methacrylate (a) / methyl methacrylate (b)
1-methoxypropanol of a glycidyl methacrylate adduct (d) of methacrylic acid copolymer (c), a / b / c / d = 46/1/10/43, weight average molecular weight: 36000), methyl ethyl ketone solution (solid Min: 45% by mass) [binder]
81.2 parts by mass- 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] [polymerization initiator]
(Product name: IRGACURE OXE-01, manufactured by BASF)
9.2 parts by mass, phenothiazine [polymerization inhibitor] 0.3 parts by mass, the following structure 1 [surfactant] 0.4 parts by mass, 1-methoxy-2-propyl acetate [solvent] 238.7 parts by mass, Methyl ethyl ketone MEK) [solvent] 321.3 parts by mass

(K pigment dispersion 1)
-Resin-coated carbon black produced in accordance with Japanese Patent No. 5320652 <0036> to <0042> 13.1% by mass
・ The following dispersant 1 0.65 mass%
・ Polymer 6.72% by mass
(Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, weight average molecular weight 37,000)
・ Propylene glycol monomethyl ether acetate
79.53 mass%

  First, the amount of K pigment dispersion 1 described in the composition of the decorative layer forming composition 1 is weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 RPM (Round Per Minutes) for 10 minutes. Solution 1 was obtained. Next, methyl ethyl ketone, 1-methoxy-2-propyl acetate, binder, phenothiazine, polymerizable compound, polymerization initiator, surfactant are weighed out, and the temperature of 25 ° C. (± 2 ° C.) is used. They were added in the order described above and stirred for 30 minutes at 150 RPM under the condition of a temperature of 24 ° C. (± 2 ° C.).

<Production of transfer film>
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Thereafter, the decorative layer forming composition 1 described above was applied and dried. In this way, a thermoplastic resin layer having a dry film thickness of 15.1 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a black decorative layer having a dry film thickness of 2.0 μm are formed on the temporary support. A composition layer was provided, and finally a protective film (12 μm thick polypropylene film) was pressure-bonded. In this way, a transfer film was produced in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the black (K) decorative layer forming composition layer, and the protective film were integrated.

(Coating solution for thermoplastic resin layer: Formulation H1)
Methanol 11.1 parts by mass Propylene glycol monomethyl ether acetate 6.36 parts by mass Methyl ethyl ketone 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) ) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.)
5.83 parts by mass-Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, weight average molecular weight = 10,000, Tg≈100 ° C.)
13.6 parts by mass 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd.)
9.1 parts by mass Fluorine-based polymer 0.54 parts by mass _{(C 6 F 13 CH 2 CH} 2 OCOCH = CH 2 40 parts of _{H (OCH (CH 3) CH} 2) 7OCOCH = CH 2 55 parts of H (OCH ₂ CH ₂ ) ₇ OCOCH = Copolymer with 5 parts of CH ₂ , weight average molecular weight 30,000, methyl ethyl ketone 30% by mass solution, manufactured by DIC, trade name: Megafac F780F)

(Coating liquid for intermediate layer: prescription P1)
-PVA205 32.2 parts by mass (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550)
・ 14.9 parts by mass of polyvinylpyrrolidone (APS Japan, K-30)
-524 parts by mass of distilled water-429 parts by mass of methanol

(2. Formation of decorative layer by transfer and patterning)
<Transfer>
On the surface of the polyester film 1 having an easy-adhesive layer on the side where the hard coat layer is not formed, the protective film is removed from the obtained transfer film, and the black decorative layer forming composition layer exposed after the removal is removed. The surface of the polyester film 1 and the surface of the polyester film 1 are overlapped with each other, and using a laminator (manufactured by Hitachi Industries (Lamic II type)), a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, a conveyance speed of 2 Laminated at 2 m / min. Subsequently, the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support.

<Patterning of decorative layer>
After peeling off the temporary support, the substrate and mask (quartz exposure mask with an image pattern that leaves only the peripheral edge of the polyester film) using a proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp Was set vertically at a distance of 200 μm between the exposure mask surface and the black decorative layer forming composition layer, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .
Next, a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) 12 times with pure water (1 part of T-PD2 and 11 parts of pure water) The mixture was diluted at 30 ° C. for 20 seconds at a flat nozzle pressure of 0.1 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, air was blown onto the upper surface of the polyester film 1 to drain the liquid, and then pure water was sprayed for 10 seconds by a shower, pure water shower washing was performed, and air was blown to reduce a liquid pool on the substrate.

  Thereafter, a sodium carbonate / sodium hydrogencarbonate developer (trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.)) is added five times with pure water (mixed in a ratio of 1 part of T-CD1 and 4 parts of pure water). The shower pressure was set to 0.1 MPa at 30 ° C. using the diluted liquid), and the decorative layer forming composition layer was developed for 30 seconds and washed with pure water.

Subsequently, using a surfactant-containing cleaning solution (trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water) at 33 ° C. for 20 seconds, cone-type nozzle pressure of 0.1 MPa The decorative layer forming composition layer was washed by spraying with a shower. Furthermore, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove residues.
Thus, the decorative film of Example 1 in which the decorative layer forming composition layer was formed on the peripheral edge on the surface where the hard coat layer was not formed was obtained.

[Evaluation]
The decorative film obtained in Example 1 was evaluated as follows. The evaluation results are shown in Tables 1 to 4 below.

<Curl value>
The decorative film was cut into a length of 50 mm and a width of 50 mm to prepare a decorative film piece as a test sample piece. Place in a heating furnace at a temperature of 150 ° C. for 30 minutes, then remove the decorative film piece, cool to room temperature, leave it on a flat place, and the distance between the surface of the flat place and the measurement target place on the decorative film piece That is, the amount of warpage of the decorative film piece was measured to obtain a curl value (H). The measurement target locations were a total of 8 points including 4 corners of the square test piece and 4 central portions of one side of the square. The curl value is the average value of the curl values measured at the above-mentioned eight measurement target locations, and the average value of the curl values measured at five test pieces is calculated, and the curl values shown in Tables 1 to 4 are calculated. It was.
When the decorative film piece curled in a convex shape with respect to a flat place after heating, the decorative film piece was inverted and arranged as a concave shape, and the curl value was measured. The results are shown in Tables 1 to 4 below.

<Punching evaluation>
The decorative film was punched 10 times, and cracking of the hard coat layer on the punched end face, peeling of the decorative layer and the base material, and the base material and the hard coat layer were evaluated according to the following criteria.
A: No cracking / peeling B: Cracking / peeling occurred once C: Cracking / peeling occurred twice D: Cracking / peeling occurred three times or more

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

<Visibility evaluation>
A hard coat film was sandwiched between polarizing plates installed in crossed Nicols so that the orientation angle was inclined by 45 ° with respect to the absorption axis of the polarizing plate, and the LED backlight was illuminated from the back, and the visibility was evaluated according to the following criteria. .
A: The rainbow unevenness cannot be seen at all. B: The rainbow unevenness is hardly visible. C: The rainbow unevenness is slightly visible but acceptable. D: The rainbow unevenness looks strong.

[Examples 2 to 16, Comparative Examples 1 to 6]
In Example 1, the thickness of the polyester film used for the substrate, the conditions of the stretching process, the presence / absence of the easy-adhesion layer, the presence / absence of the hard coat layer, and the composition of the hard coat layer are as shown in Tables 1 to 4 below. Except having changed, it carried out similarly to Example 1, and manufactured the decorative film of each Example and the comparative example. Moreover, in Example 16, it replaced with the uniaxially stretched polyester film, the biaxially stretched polyethylene film formed on the following conditions was used as a base material, and it replaced with a polyester film in the comparative example 1-comparative example 4, and shows below. A resin substrate was used.

Details of the base film used in Example 16 and Comparative Examples 1 to 4 are as follows.
-Biaxially stretched PET-
In the polyester film used in Example 1, in addition to stretching in the TD direction, a biaxially stretched polyester film stretched in the MD direction at a stretch ratio of 3.2 times was obtained to obtain a base film.
-PC-
Polycarbonate (PC) film: Sumika Acrylic Sales Co., Ltd., Technoloy C1000 (trade name), thickness 150 μm
-PMMA-
Polymethylmethacrylate (PMMA) film: Sumika Acrylic Sales Co., Ltd., Technoloy S1000 (trade name), thickness 150 μm
-PMMA / PC / PMMA-
Film in which PMMA / PC / PMMA is laminated in this order, Sumika Acrylic Sales Co., Ltd., Technoloy C-101 (trade name), thickness 300 μm

The formulation of the hard coat layer forming composition 2 used in Examples 15 to 17 is as follows.
(Composition of composition 2 for forming hard coat layer: used in Example 15)
・ 3,4-epoxycyclohexylmethyl acrylate [a) component]
39 parts by mass · DPHA: KAYARD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
[Component b] 55.4 parts by mass Irgacure 127: alkylphenone photopolymerization initiator (BASF (manufactured))
[Component c] 2.5 parts by mass Irgacure 290: sulfonium salt cationic polymerization initiator (BASF (manufactured))
[D) Ingredient] 2.0 parts by mass / FP-1 [wind unevenness inhibitor] 0.10 parts by mass / RS-90 (trade name, DIC Corporation) [antifouling agent] 1.0 part by mass / solvent : MEK 200 parts by mass ・ Solvent: MIBK 100 parts by mass

(Composition of composition 3 for forming hard coat layer: used in Examples 16 to 17)
・ 3,4-epoxycyclohexylmethyl acrylate [a) component]
12.0 parts by mass · DPHA: KAYARD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
[Component b] 83.0 parts by mass Irgacure 127: alkylphenone photopolymerization initiator (BASF (manufactured))
[Component c] 3.7 parts by mass · Irgacure 290: sulfonium salt-based cationic polymerization initiator (BASF (manufactured)) [d) component] 1.2 parts by mass · FP-1 [anti-wind unevenness inhibitor] 0.10 parts by mass Parts / solvent: 200 parts by mass of MEK / solvent: 100 parts by mass of MIBK

From the evaluation results shown in Tables 1 to 4, the decorative film of the example whose curl value after a heat history at 150 ° C. for 30 minutes is 5 mm or less, and the heat shrinkage rate (150 ° C. for 30 minutes) are 3.0%. The decorative films of the examples using the following polyester films as the base materials all have better scratch resistance than the decorative films of the comparative examples, and cracks, cracks, and peeling between layers during punching It turns out that generation | occurrence | production of is suppressed.
Especially, 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 was further improved.

The disclosure of Japanese Patent Application No. 2006-029017 filed on February 18, 2016 is incorporated herein by reference.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims (19)

It is a decorative film having a polyester film, a decorative layer, and a hard coat layer,
A decorative film in which a curl value of the decorative film generated when a thermal history at a temperature of 150 ° C. for 30 minutes is given to a film piece having a length of 50 mm and a width of 50 mm of the decorative film is 5 mm or less.   The decorating film of Claim 1 which has the said decorating layer in at least one part with respect to the whole area | region in the planar view of the said decorating film.   The decorative film according to claim 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. It is a decorative film having a polyester film, a decorative layer, and a hard coat layer,
The polyester film is a uniaxially oriented polyester film,
When the polyester film was given a heat history at a temperature of 150 ° C. for 30 minutes, the thermal shrinkage rate in one direction in the plane of the polyester film and in the direction perpendicular to the one direction in the plane was 3.0%. A decorative film that is: The decorative layer, the disposed on one surface of a polyester film, the hard coat layer, the polyester claim decorative layer is disposed on the opposite side to the arranged surface of the film 4 The decorative film described in 1. The decorative film according to claim 4 or 5 , wherein the decorative layer has at least a part of the decorative layer with respect to the entire region in a plan view of the decorative film. The thickness of the polyester film, decorative film according to any one of claims 4 to claim 6 is 40Myuemu～500myuemu. The decorative film according to any one of claims 4 to 7 , wherein an in-plane retardation Re of the polyester film at a measurement wavelength of 589 nm is in a range of 3000 nm to 50000 nm. The ratio of the in-plane retardation Re at the measurement wavelength of 589 nm of the polyester film to the retardation Rth in the thickness direction at the measurement wavelength of 589 nm of the polyester film is in the range of 0.6 to 1.2. 9. The decorative film according to any one of items 8 . The decorative film according to any one of claims 4 to 9 , wherein an easy-adhesion layer is provided on at least one surface of the polyester film. The decorative film according to any one of claims 4 to 10 , wherein the hard coat layer has a pencil hardness of H or more. The decorative film according to any one of claims 4 to 11 , wherein the hard coat layer has a thickness of 5 µm or more. The hard coat layer includes at least a structure derived from the following a), a structure derived from the following b), the following c) and the following d),
15% by mass to 70% by mass of the structure derived from the following a), 25% by mass to 80% by mass of the structure derived from the following b), and 0.1% by mass of the following c) based on the total solid content of the hard coat layer. The decorative film according to any one of claims 4 to 12 , comprising 10% by mass to 10% by mass and 0.1% by mass to 10% by mass of the following d).
a) a compound having one alicyclic epoxy group and one group containing an ethylenically unsaturated double bond in the molecule and having a molecular weight of 300 or less; b) three or more ethylenic groups in the molecule. Compound having group containing saturated double bond c) radical polymerization initiator d) cationic polymerization initiator An image display device comprising the image display element and the decorative film according to any one of claims 1 to 13 , wherein the decorative film is provided on an outermost surface. A touch panel comprising the decorative film according to any one of claims 1 to 13 , and comprising the decorative film on an outermost surface. Using a tenter type stretching device including a plurality of clips respectively traveling along a pair of rails installed on both sides of the film conveyance path, the unstretched polyester film is gripped by the clips with respect to the film conveyance path. A transverse stretching step for stretching in a direction perpendicular to the heat treatment, a heat setting step for heat setting by heating the polyester film after the transverse stretching, heating the polyester film after the heat setting step, and A thermal relaxation step of narrowing the length in the direction perpendicular to the film transport direction and 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 setting step is 0.1% to 7%, and the relaxation rate in the direction orthogonal to the film transport direction is 0.1%. A uniaxially oriented polyester film having a heat shrinkage rate of 3.0% or less at a temperature of 150 ° C. for 30 minutes in a direction perpendicular to the film transport direction and the film transport direction as ˜7% Forming a polyester film,
Including a hard coat layer forming step, forming a hard coat layer on at least one surface on at least a portion the decorative layer a decorative layer forming step of forming a well the uniaxially oriented polyester film, on one side of the uniaxially oriented polyester film A method for producing a decorative film. Narrowing the length in the direction orthogonal to the film transport direction of the polyester film in the heat relaxation step includes narrowing the distance between the pair of rails installed on both sides of the film transport path,
The method for producing a decorative film according to claim 16 , wherein reducing the length of the polyester film in the film conveyance direction in the heat relaxation step includes narrowing a distance between the plurality of traveling clips. To reduce the film length in the conveying direction of the polyester film of the thermal relaxation step, under tension in the film conveying direction of the polyester film, according to claim 16 or comprising reduce the length while conveying in warm conditions The manufacturing method of the decorating film of Claim 17 . In the heat relaxation step, the transport tension of the polyester film is 10 N / m width to 80 N / m width,
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,
During cooling after the reduced length of the polyester film, the film surface temperature of the polyester film, 70 ° C. cooling rate in the range of ± 20 ° C. the claims 16 to be 100 ℃ / min~2000 ℃ / min The manufacturing method of the decorating film of any one of Claim 18 .