KR20220136902A - Hard coat film, optical member, and image display device - Google Patents

Abstract

Provided are a hard coat film, an optical member, and an image display device which has high hardness, suppressed curling, and high adhesion between a visual side surface and the other layer. In order to achieve the purpose, the hard coat films (100a, 100b) of the present invention includes a substrate (110), a first hard coat layer (101), a second hard coat layer (102), and a third hard coat layer (103). The first hard coat layer (101), the second hard coat layer (102), the substrate, and the third hard coat layer (103) are sequentially laminated on a visual side. In addition, each of the first hard coat layer (101) and the second hard coat layer (102) includes nano silica particles. Moreover, a weight average particle diameter of the nano silica particle (101P) included in the first hard coat layer (101) is larger than the weight average particle diameter of the nano silica particle (102P) included in the second hard coat layer (102).

Description

A hard coat film, an optical member, and an image display apparatus TECHNICAL FIELD {HARD COAT FILM, OPTICAL MEMBER, AND IMAGE DISPLAY DEVICE}

The present invention relates to a hard coat film, an optical member, and an image display device.

A hard-coat film is the film which formed the hard-coat layer in the film surface and improved abrasion resistance etc., and is widely used for image display apparatuses (patent document 1 etc.).

Japanese Laid-Open Patent Publication No. 2008-221746

However, when the hardness of a hard-coat layer is made high, there exists a possibility that curl may arise in a hard-coat film by cure shrinkage. On the other hand, when cure shrinkage is reduced, there exists a possibility that the hardness of a hard-coat layer may become low. That is, in a hard-coat film, there exists a problem that hardness and suppression of curl are a trade-off.

Moreover, other layers, such as an antireflection layer, may be laminated|stacked and used on the visual recognition side surface of a hard-coat layer further. However, when the hardness of the hard-coat layer surface is made high, there exists a possibility that the adhesiveness of the visual recognition side surface and another layer may fall.

Then, this invention has high hardness, Curl|Karl is suppressed, and it aims at providing the hard-coat film with high adhesiveness of the visual recognition side surface and another layer, an optical member, and an image display apparatus.

In order to achieve the above object, the hard coat film of the present invention,

a base material, a first hard coat layer, a second hard coat layer, and a third hard coat layer;

The first hard coat layer, the second hard coat layer, the base material, and the third hard coat layer are laminated in this order on the visual side,

The first hard coat layer and the second hard coat layer each contain nano silica particles,

The weight average particle diameter of the said nano-silica particle contained in the said 1st hard-coat layer is larger than the weight average particle diameter of the said nano-silica particle contained in the said 2nd hard-coat layer, It is characterized by the above-mentioned.

The optical member of this invention is an optical member containing the hard coat film of this invention.

The image display apparatus of this invention is an image display apparatus containing the hard coat film of this invention, or the optical member of this invention.

ADVANTAGE OF THE INVENTION According to this invention, hardness is high, Curl|Karl is suppressed, and the hard-coat film with high adhesiveness of the visual recognition side surface and another layer, an optical member, and an image display device can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which illustrates the structure of the hard-coat film of this invention.
It is sectional drawing which shows the example in which the hard-coat film of this invention was laminated|stacked on the glass plate.
It is process sectional drawing which illustrates the manufacturing process of the hard-coat film of this invention.

Next, the present invention will be described more specifically by way of example. However, this invention is not limited at all by the following description.

The hard-coat film of this invention does not need to contain a nano silica particle, for example in the said 3rd hard-coat layer.

As for the hard coat film of this invention, the thickness of a said 3rd hard-coat layer may be smaller than the total thickness of the thickness of a said 1st hard-coat layer, and the thickness of a said 2nd hard-coat layer, for example.

In the hard coat film of the present invention, for example, the weight average particle diameter of the nano silica particles contained in the first hard coat layer is 30 to 50 nm, and the nano silica particles contained in the second hard coat layer. 5-30 nm may be sufficient as a weight average particle diameter.

As for the hard coat film of this invention, 90 % or more may be sufficient as the light transmittance in wavelength 550nm of the said whole hard coat film, for example.

A polarizing plate may be sufficient as the optical member of this invention, for example.

In the present invention, "weight" and "mass" may be read interchangeably unless otherwise specified. For example, "parts by mass" may be read as "parts by weight", "parts by weight" may be read as "parts by mass", "mass %" may be read as "parts by weight", and " Weight %" may be read as "mass %".

[One. hard coat film]

As for the hard coat film of this invention, as above-mentioned, the weight average particle diameter of the said nano silica particle contained in the said 1st hard-coat layer is more than the weight average particle diameter of the said nano-silica particle contained in the said 2nd hard-coat layer. Big. That is, the weight average particle diameter of the nano silica particles contained in the first hard coat layer and the weight average particle diameter of the nano silica particles contained in the second hard coat layer satisfy the relationship of the following formula (1) .

Ra > Rb (One)

In said Formula (1), Ra is the weight average particle diameter [nm] of the said nano silica particle contained in the said 1st hard-coat layer. Rb is the weight average particle diameter [nm] of the said nano silica particle contained in the said 2nd hard-coat layer.

An example of the structure of the hard coat film of this invention is shown in sectional drawing of Fig.1 (a). As shown, this hard coat film 100a includes a base material 110 , a first hard coat layer 101 , a second hard coat layer 102 , and a third hard coat layer 103 . do. And as shown, the 1st hard-coat layer 101, the 2nd hard-coat layer 102, the base material 110, and the 3rd hard-coat layer 103 are laminated|stacked in this order from the visual recognition side. has been In other words, the second hard coat layer 102 and the first hard coat layer 101 are laminated in this order on one surface (viewing side) of the base material 110 , and the other side of the base material 110 is The third hard coat layer 103 is laminated on the surface (the surface on the viewing back side). The 1st hard-coat layer 101 contains the nano silica particle 101P. The 2nd hard-coat layer 102 contains the nano silica particle 102P. And the weight average particle diameter (Ra of the said Formula (1)) of the nano-silica particle 101P contained in the 1st hard-coat layer 101 is nano-silica particle 102P contained in the 2nd hard-coat layer 102 ) is larger than the weight average particle diameter of (Rb in the above formula (1)).

Moreover, another example of the structure of the hard coat film of this invention is shown in sectional drawing of FIG.1(b). As shown, this hard coat film 100b is the same as that of the hard coat film 100a of FIG. 1(a), except that the 3rd hard coat layer 103 contains the nano silica particle 103P. .

As mentioned above, the hard coat film of this invention has high hardness and the curl is suppressed. Specifically, for example, curl is suppressed by laminating hard coat layers on both sides of the substrate, and the first hard coat layer and the second hard coat layer are laminated on the surface side (visible side). Therefore, the hardness is high. For this reason, the hard coat film of this invention can not only be used as a member of a polarizing plate, but can be used also as a front plate, for example.

The hard coat film of the present invention can be used, for example, as a clear film or an anti-glare film (also referred to as an AG film). For example, in order to use it as an anti-glare film, what is necessary is just to give anti-glare property (AG property) to the outermost layer (for example, the said 1st hard-coat layer) by the visual recognition side.

Moreover, the hard coat film of this invention may contain other layers other than the said base material, a said 1st hard-coat layer, a said 2nd hard-coat layer, and a said 3rd hard-coat layer, and does not need to contain it. For example, the base material, the first hard coat layer, the second hard coat layer, and the third hard coat layer may each be directly laminated, or may be laminated through another layer such as an adhesive layer. do. Moreover, for example, as for the said 1st hard-coat layer and the said 3rd hard-coat layer, the other layer may be laminated|stacked on the outer side, respectively, and it does not need to be laminated|stacked. Specifically, for example, an antireflection effect may be imparted by laminating an antireflection layer (also referred to as an AR layer) as another layer on the outside of the first hard coat layer. Although the said antireflection layer is not specifically limited, For example, a DRY-AR layer (AR layer formed by dry methods, such as sputtering method and vapor deposition method) may be sufficient. Moreover, the adhesive bonding layer may be formed in the outer side of the said 3rd hard-coat layer, for example. The said other layer can be formed by coating, for example. As mentioned above, the hard coat film of this invention has high adhesiveness of the visual recognition side surface and another layer. More specifically, since the hard coat film of this invention has high adhesiveness between the surface of the said 1st hard-coat layer (the weight average particle diameter of a nano silica particle is large), and another layer, for example, the said 1st hard-coat layer, for example. It is suitable for forming an antireflection layer (for example, a DRY-AR layer) as another layer thereon. Moreover, the hard coat film of this invention is, for example, between the said 1st hard coat layer (the weight average particle diameter of a nano silica particle is large) and the said base material, The said 2nd hard coat layer (weight average particle diameter of a nano silica particle) is small) exists, the hardness is high. Moreover, since curl is suppressed as mentioned above, the hard coat film of this invention has favorable conveyability, when forming another layer by coating.

In addition, in this invention, "adhesive adhesive layer" means "adhesive layer or adhesive layer." "Adhesive layer" means "a layer formed with an adhesive". "Adhesive layer" means "a layer formed with an adhesive." In general, there is a case where the adhesive force (adhesive force) is relatively small and re-peelable of the adherend is called “adhesive”, and the case where re-peelability of the adherend is impossible or difficult because the adhesive force (adhesive force) is relatively large is called “adhesive” and distinguishes it. have. In the present invention, a thing with a relatively small adhesive force (adhesive force) is called an "adhesive", and a thing with a relatively large adhesive force (adhesive force) is called an "adhesive", but there is no clear distinction between the two.

The hard coat film of this invention WHEREIN: The material of the said base material, a said 1st hard-coat layer, a said 2nd hard-coat layer, and a said 3rd hard-coat layer is not specifically limited, For example, a general hard-coat film may be the same as or according to it. About a specific example, it illustrates in the manufacturing method of the hard-coat film of this invention mentioned later. The said nano silica particle is not specifically limited, either, For example, you may follow it similarly to a general hard-coat film, or it. For the hard coat film of the present invention, for example, the same material as that of a general hard coat film can be used in this way (no special material, processing, etc. are required), without sacrificing appearance, display characteristics, etc., hardness It is compatible with the suppression of the height of the curl.

In recent years, for example, in a note PC display, also in a large size display, attaching a touch sensor in a liquid crystal cell (in-cell formation of a touch sensor) is implemented. Moreover, for example, a note PC display WHEREIN: From a viewpoint of light weight, thinness, and workability, a glassless structure (structure which does not use glass for a display) is calculated|required. For example, the hard coat film of this invention may satisfy these requests because hardness is high.

Although the said 3rd hard-coat layer in the hard-coat film of this invention may contain the nano silica particle, as mentioned above, it does not need to contain a nano silica particle. Since the hardness of a hard-coat film becomes higher easily that the said 3rd hard-coat layer does not contain a nano silica particle, it is preferable. When the said 3rd hard-coat layer does not contain a nano silica particle, for example, the crack (crack) by bending does not generate|occur|produce easily in the said 3rd hard-coat layer. In addition, if the third hard coat layer does not contain nano silica particles, for example, even if a thick adhesive layer is formed on the outside of the third hard coat layer, the third hard coat layer is caused by scratches or the like. Cracks rarely occur. Moreover, when a said 3rd hard-coat layer does not contain a nano silica particle, material cost can be suppressed largely and there also exists an advantage, such as the workability of a hard-coat film improving.

In the present invention, the thickness of the substrate is not particularly limited, but from the viewpoints of workability such as strength and handleability and thin layer properties, for example, 80 µm or more, 90 µm or more, 100 µm or more, 110 µm or more, or 120 µm or more, for example, 60 µm or less, 50 µm or less, 40 µm or less, 30 µm or less, or 20 µm or less, for example, 10 to 40 µm, 40 to 70 µm, 70-100 micrometers, 100-130 micrometers, or 130-160 micrometers may be sufficient. It is preferable that the thickness of the said base material is not too large from a viewpoint of thin layer property, and it is preferable that it is not too small from a viewpoint of hardness maintenance.

In the present invention, the thickness of the first hard coat layer is not particularly limited, and for example, 0.1 µm or more, 1 µm or more, 2 µm or more, 3 µm or more, 4 µm or more, 5 µm or more, 6 µm or more. or more, 7 μm or more, 8 μm or more, 9 μm or more, or 10 μm or more, for example, 30 μm or less, 20 μm or more, 10 μm or more, 5 μm or less, 4 μm or less, 3 μm or less, 2 Micrometer or less, or 1 micrometer or less may be sufficient, for example, 0.1-30 micrometers, 0.1-20 micrometers, 0.1-10 micrometers, 0.1-5 micrometers, 1-30 micrometers, 1-20 micrometers, 1-10 micrometers, 1 5 to 5 µm, 5 to 30 µm, 5 to 20 µm, 5 to 10 µm, 0.1 to 1 µm, 1 to 5 µm, 5 to 10 µm, 10 to 20 µm, or 20 to 30 µm may be sufficient. It is preferable that the thickness of a said 1st hard-coat layer is not too large from a viewpoint of workability and a flexibility, and it is preferable that it is not too small from a viewpoint of hardness.

In the present invention, the thickness of the second hard coat layer is not particularly limited, but may be, for example, 0.1 µm or more, 1 µm or more, 2 µm or more, 3 µm or more, 4 µm or more, or 5 µm or more. , for example, 50 μm or less, 30 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, or 1 μm or less, for example For example, 0.1 to 50 µm, 0.1 to 30 µm, 0.1 to 20 µm, 0.1 to 10 µm, 0.1 to 5 µm, 1 to 50 µm, 1 to 30 µm, 1 to 20 µm, 1 to 10 µm, 5 to 50 micrometer, 5-30 micrometers, 5-20 micrometers, 10-50 micrometers, 0.1-1 micrometer, 1-5 micrometers, 5-10 micrometers, 10-20 micrometers, or 20-50 micrometers may be sufficient. It is preferable that the thickness of a said 2nd hard-coat layer is not too large from a viewpoint of workability and a flexibility, and it is preferable that it is not too small from a viewpoint of hardness.

In the present invention, the thickness of the third hard coat layer is not particularly limited, but may be, for example, 0.1 µm or more, 1 µm or more, 2 µm or more, 3 µm or more, 4 µm or more, or 5 µm or more. , for example, 50 μm or less, 30 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, or 1 μm or less, for example For example, 0.1 to 50 µm, 0.1 to 30 µm, 0.1 to 20 µm, 0.1 to 10 µm, 0.1 to 5 µm, 1 to 50 µm, 1 to 30 µm, 1 to 20 µm, 1 to 10 µm, 5 to 50 micrometer, 5-30 micrometers, 5-20 micrometers, 10-50 micrometers, 0.1-1 micrometer, 1-5 micrometers, 5-10 micrometers, 10-20 micrometers, or 20-50 micrometers may be sufficient. It is preferable that the thickness of a said 3rd hard-coat layer is not too large from a viewpoint of workability and a flexibility, and it is preferable that it is not too small from a viewpoint of hardness.

Moreover, in the hard coat film of this invention, when the thickness of the arbitrary layer containing a base material is not uniform (for example, when the surface of a layer has an unevenness|corrugation), the "thickness" of the layer is an average make it thick

As for the hard coat film of this invention, as mentioned above, the thickness of a said 3rd hard-coat layer may be smaller than the total thickness of the thickness of a said 1st hard-coat layer, and the thickness of a said 2nd hard-coat layer, for example. . That is, the thickness of a said 1st hard-coat layer, the thickness of a said 2nd hard-coat layer, and the thickness of a said 3rd hard-coat layer may satisfy|fill the relationship of following Numerical formula (2). Thus, by making the thickness of a said 3rd hard-coat layer small, for example, the total thickness of a hard-coat film can be made small, the weight reduction of the whole hard-coat film is possible, improvement of the workability of a hard-coat film, material cost There are effects such as suppression of cracks (cracks) at the time of bending of the hard coat film.

Tab > Tc (2)

In said Numerical formula (2), Tab is the sum total [micrometer] of the thickness of the said 1st hard-coat layer, and the thickness of a said 2nd hard-coat layer. Tc is the thickness [micrometer] of the said 3rd hard-coat layer.

The hard coat film of the present invention, as described above, for example, by forming an antireflection layer on the first hard coat layer having a large weight average particle diameter of the nano silica particles, the hard coat layer and the antireflection layer (for example, DRY-AR layer) has high adhesion. Moreover, hardness is high because the said 2nd hard-coat layer with a small weight average particle diameter of a nano silica particle exists between the said 1st hard-coat layer and the said base material, for example in the hard-coat film of this invention.

In addition, in this invention, "nano silica particle" means the silica particle whose weight average particle diameter is about several hundred nm or less. In the present invention, the weight average particle diameter of the "nano silica particles" is not particularly limited, but for example, 1 nm or more, 10 nm or more, 50 nm or more, 100 nm or more, 150 nm or more, 200 nm or more, or It may be 250 nm or more, for example, 300 nm or less, 250 nm or less, 200 nm or less, 100 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less, or 10 nm or less, e.g. For example, 1-300 nm, 1-250 nm, 1-200 nm, 1-100 nm, 1-50 nm, 10-300 nm, 10-250 nm, 10-200 nm, 10-100 nm, 50- 300 nm, 50-250 nm, 50-200 nm, 50-100 nm, 100-300 nm, 100-250 nm, 1-10 nm, 10-50 nm, 50-100 nm, 100-200 nm, or 200 -300 nm may be sufficient.

In addition, in this invention, although the measuring method of a weight average particle diameter is although it does not specifically limit, For example, it is as follows. For example, the average particle diameter of the nanoparticles in a hard-coat layer can be measured by TEM (Transmission Electron Microscope, transmission electron microscope) analysis of the cross section of the said hard-coat layer, This can be estimated as a weight average particle diameter. Specifically, a value obtained by averaging the particle diameters of all particles observed in the 0.5 μm × 0.5 μm region in the TEM image of the cross-section (the number obtained by adding the major and minor diameters and dividing by 2) can be estimated as the weight average particle diameter. . Moreover, when measuring the weight average particle diameter of the said nanoparticle system in the material (solution) in which the nanoparticles are disperse|distributed, it can measure using the light scattering and diffraction method, for example.

In this invention, although the weight average particle diameter of the said nano silica particle contained in the said 1st hard-coat layer is not specifically limited, For example, 1 nm or more, 10 nm or more, 50 nm or more, 100 nm or more, 150 Nanometer or more, 200 nm or more, or 250 nm or more, for example, 300 nm or less, 250 nm or less, 200 nm or less, 100 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less, Or 10 nm or less may be sufficient, for example, 1-300 nm, 1-250 nm, 1-200 nm, 1-100 nm, 1-50 nm, 10-300 nm, 10-250 nm, 10-200 nm , 10-100 nm, 50-300 nm, 50-250 nm, 50-200 nm, 50-100 nm, 100-300 nm, 100-250 nm, 1-10 nm, 10-50 nm, 50-100 nm , 100 to 200 nm, or 200 to 300 nm may be sufficient. The weight average particle diameter of the nano silica particles contained in the first hard coat layer is preferably not too large from the viewpoint of transparency of the film, and preferably not too small from the viewpoint of adhesion with the antireflection layer (AR layer). .

In this invention, although the weight average particle diameter of the said nano silica particle contained in the said 2nd hard-coat layer is not specifically limited, For example, 1 nm or more, 10 nm or more, 50 nm or more, 100 nm or more, 150 Nanometer or more, 200 nm or more, or 250 nm or more, for example, 300 nm or less, 250 nm or less, 200 nm or less, 100 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less, Or 10 nm or less may be sufficient, for example, 1-300 nm, 1-250 nm, 1-200 nm, 1-100 nm, 1-50 nm, 10-300 nm, 10-250 nm, 10-200 nm , 10-100 nm, 50-300 nm, 50-250 nm, 50-200 nm, 50-100 nm, 100-300 nm, 100-250 nm, 1-10 nm, 10-50 nm, 50-100 nm , 100 to 200 nm, or 200 to 300 nm may be sufficient. It is preferable that the weight average particle diameter of the said nano silica particle contained in the said 2nd hard-coat layer is not too large from a viewpoint of transparency of a film, and it is preferable that it is not too small from a viewpoint of hardness of a film.

As mentioned above, the said 3rd hard-coat layer may contain the nano silica particle, and does not need to contain it. When the nano silica particles are contained in the third hard coat layer, the weight average particle diameter of the nano silica particles is not particularly limited, but for example, 1 nm or more, 10 nm or more, 50 nm or more, 100 nm or more, 150 nm or more, 200 nm or more, or 250 nm or more may be sufficient, for example, 300 nm or less, 250 nm or less, 200 nm or less, 100 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less or 10 nm or less, for example, 1-300 nm, 1-250 nm, 1-200 nm, 1-100 nm, 1-50 nm, 10-300 nm, 10-250 nm, 10-200 nm, 10-100 nm, 50-300 nm, 50-250 nm, 50-200 nm, 50-100 nm, 100-300 nm, 100-250 nm, 1-10 nm, 10-50 nm, 50-100 nm, 100-200 nm, or 200-300 nm may be sufficient. It is preferable that the weight average particle diameter of the said nano silica particle contained in the said 3rd hard-coat layer is not too large from a viewpoint of transparency of a film, and it is preferable that it is not too small from a viewpoint of hardness of a film.

In the hard coat film of the present invention, for example, as described above, the weight average particle diameter of the nano silica particles contained in the first hard coat layer is 30 to 50 nm, and the second hard coat layer contains 5-30 nm may be sufficient as the weight average particle diameter of the said nano silica particle.

Moreover, the said 1st hard-coat layer WHEREIN: The content rate of the said nano silica particle is 1 mass % or more, 20 mass % or more, 30 mass with respect to the mass (weight) of the whole said 1st hard-coat layer, for example. % or more, 40 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, or 90 mass% or more, for example, less than 100 mass%, 90 mass% or less; 80 mass % or less, 70 mass % or less, 60 mass % or less, 50 mass % or less, 40 mass % or less, 30 mass % or less, or 20 mass % or less may be sufficient, For example, 1-90 mass %, 1- 80 mass%, 1 to 70 mass%, 1 to 60 mass%, 1 to 50 mass%, 1 to 40 mass%, 20 to 90 mass%, 20 to 80 mass%, 20 to 70 mass%, 20 to 60 mass% %, 20-50 mass%, 30-90 mass%, 30-80 mass%, 30-70 mass%, 30-60 mass%, 30-50 mass%, 30-40 mass%, 40-90 mass%, 40 to 80 mass%, 40 to 70 mass%, 40 to 50 mass%, 60 to 90 mass%, 1 to 20 mass%, 20 to 40 mass%, 40 to 60 mass%, 60 to 80 mass%, or 80 -90 mass % may be sufficient. The said 1st hard-coat layer WHEREIN: It is preferable that the content rate of the said nano silica particle is not too large from a viewpoint of workability and a flexibility, and it is preferable that it is not too small from a viewpoint of hardness.

The said 2nd hard-coat layer WHEREIN: The content rate of the said nano silica particle is 1 mass % or more, 20 mass % or more, 30 mass % or more with respect to the mass (weight) of the whole said 2nd hard-coat layer, for example. , 40 mass % or more, 50 mass % or more, 60 mass % or more, 70 mass % or more, 80 mass % or more, or 90 mass % or more may be sufficient, for example, less than 100 mass %, 90 mass % or less, 80 mass % % or less, 70 mass% or less, 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, or 20 mass% or less, for example, 1-90 mass%, 1-80 mass %, 1 to 70 mass%, 1 to 60 mass%, 1 to 50 mass%, 1 to 40 mass%, 20 to 90 mass%, 20 to 80 mass%, 20 to 70 mass%, 20 to 60 mass%, 20-50 mass%, 30-90 mass%, 30-80 mass%, 30-70 mass%, 30-60 mass%, 30-50 mass%, 30-40 mass%, 40-90 mass%, 40- 80 mass%, 40-70 mass%, 40-50 mass%, 60-90 mass%, 1-20 mass%, 20-40 mass%, 40-60 mass%, 60-80 mass%, or 80-90 mass% It may be mass %. The said 2nd hard-coat layer WHEREIN: It is preferable that the content rate of the said nano silica particle is not too large from a viewpoint of workability and a flexibility, and it is preferable that it is not too small from a viewpoint of hardness.

The said 3rd hard-coat layer WHEREIN: The content rate of the said nano silica particle is 1 mass % or more, 20 mass % or more, 30 mass % or more with respect to the mass (weight) of the whole said 3rd hard-coat layer, for example. , 40 mass % or more, 50 mass % or more, 60 mass % or more, 70 mass % or more, 80 mass % or more, or 90 mass % or more may be sufficient, for example, less than 100 mass %, 90 mass % or less, 80 mass % % or less, 70 mass% or less, 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, or 20 mass% or less, for example, 1-90 mass%, 1-80 mass %, 1 to 70 mass%, 1 to 60 mass%, 1 to 50 mass%, 1 to 40 mass%, 20 to 90 mass%, 20 to 80 mass%, 20 to 70 mass%, 20 to 60 mass%, 20-50 mass%, 30-90 mass%, 30-80 mass%, 30-70 mass%, 30-60 mass%, 30-50 mass%, 30-40 mass%, 40-90 mass%, 40- 80 mass%, 40-70 mass%, 40-50 mass%, 60-90 mass%, 1-20 mass%, 20-40 mass%, 40-60 mass%, 60-80 mass%, or 80-90 mass% It may be mass %. The said 3rd hard-coat layer WHEREIN: It is preferable that the content rate of the said nano silica particle is not too large from a viewpoint of workability and a flexibility, and it is preferable that it is not too small from a viewpoint of hardness.

As mentioned above, 90 % or more of the light transmittance in wavelength 550nm of the said whole hard coat film may be sufficient as the hard coat film of this invention, for example. The light transmittance in wavelength 550nm of the said whole hard coat film is 90 % or more, 92 % or more, 94 % or more, 95 % or more, 96 % or more, 97 % or more, 98 % or more, or 99, for example. % or more, for example, 100% or less, 99% or less, 98% or less, 97% or less, 96% or less, 95% or less, 94% or less, 93% or less, 92% or less, or 90% or less For example, 90-100%, 90-99%, 90-98%, 90-97%, 90-96%, 90-95%, 90-94%, 90-93%, 90-92% , 92-100%, 92-99%, 92-98%, 92-97%, 92-96%, 92-95%, 92-94%, 92-93%, 94-100%, 94-99% , 94-98%, 94-97%, 94-96%, 94-95%, 95-100%, 95-99%, 95-98%, 95-97%, 95-96%, 96-100% , 96 to 99%, 96 to 98%, 96 to 97%, 97 to 100%, 97 to 99%, 97 to 98%, 98 to 100%, 98 to 99%, or 99 to 100%. When the light transmittance of the whole hard coat film is high, for example, when it turns into a polarizing plate, it does not impair brightness, and since transparency is high, there exists an advantage, such as being easy to perform an external appearance inspection.

In addition, in this invention, although the measuring method of a light transmittance is although it does not specifically limit, For example, it can measure with the following measuring method.

[Method for measuring light transmittance]

Device: Integral Sphere Spectral Transmittance Meter (Product Name: DOT-3C, Murakami Color Technology Research Institute Manufactured)

・Measurement mode: total light transmittance & color calculation

Light source: D65 light source

·Viewing angle: 2 degree field of view

- The light transmittance in wavelength 550nm is measured on the measurement conditions of 23 degreeC of temperature and 50% of humidity by the above setting.

[2. Manufacturing method of hard coat film]

The manufacturing method of the hard coat film of this invention is not specifically limited, For example, it can carry out similarly to the manufacturing method of a general hard coat film, and can implement. Below, the manufacturing method of the hard-coat film of this invention is given and demonstrated.

An example of the manufacturing method of the hard-coat film of this invention is shown in process sectional drawing of FIG.3(a)-(d).

First, as shown to Fig.3 (a), the base material 110 is prepared, and the 3rd hard-coat layer 103 is formed in the one surface.

Although the base material 110 in particular is not restrict|limited, For example, a light transmissive base material may be sufficient, Specifically, For example, a transparent plastic film base material etc. are mentioned, for example. The transparent plastic film substrate is not particularly limited, but is preferably excellent in visible light transmittance (preferably light transmittance of 90% or more) and excellent in transparency (preferably haze value of 1% or less), and yes For example, the transparent plastic film base material of Unexamined-Japanese-Patent No. 2008-90263 is mentioned. As the transparent plastic film substrate, one having optically little birefringence is preferably used. The hard coat film of the present invention may be used, for example, in a polarizing plate as a protective film, and in this case, as the transparent plastic film substrate, triacetyl cellulose (TAC), polycarbonate, acrylic polymer, cyclic to nor A film formed of polyolefin or the like having a bornene structure is preferable. Moreover, in this invention, the said transparent plastic film base material may be the polarizer itself. With such a structure, since the structure of a polarizing plate can be simplified by making the protective layer which consists of TAC etc. unnecessary, the manufacturing process number of a polarizing plate or an image display apparatus is reduced, and the improvement of production efficiency is attained. Moreover, if it is such a structure, a polarizing plate can be made thin more. In addition, when the transparent plastic film substrate is a polarizer, for example, the non-transparent layer serves as a protective layer. Moreover, if it is such a structure, when it attaches to the liquid crystal cell surface, for example, the hard coat film of this invention will serve as a cover plate.

Although the thickness in particular of the said base material is not restrict|limited in this invention, For example, it is as above-mentioned. The refractive index in particular of the said base material is not restrict|limited. The refractive index is, for example, in the range of 1.30 to 1.80 or 1.40 to 1.70.

In addition, in this invention, unless otherwise indicated, "refractive index" means the refractive index of wavelength 550nm. Moreover, in this invention, although the measuring method of refractive index is although it does not specifically limit, In the case of refractive index of fine substances, such as particle|grains, it can measure using the Beckett method, for example. The Beckett method is a measurement method in which a measurement sample is dispersed in a standard refractive solution on a slide glass, and the refractive index of the standard refractive solution when the outline of the sample disappears or becomes blurred when observed under a microscope is used as the refractive index of the sample. In addition, the measuring method of the refractive index of the measuring object (for example, the resin which comprises an anti-glare film, an anti-glare layer, or an anti-glare layer, etc.) which cannot measure a refractive index by the Beckett method is not specifically limited, For example, It can measure using a general refractometer (instrument for refractive index measurement). Although the said refractometer is not specifically limited, either, For example, Abbe refractometer etc. are mentioned. As said Abbe refractometer, the multi-wavelength Abbe refractometer DR-M2/1550 (brand name) by the Atago Co., Ltd. product is mentioned, for example.

Although the method of forming the 3rd hard-coat layer 103 on the base material 110 is not specifically limited, For example, it is as follows. Hereinafter, the process of forming this 3rd hard-coat layer 103 may be called "the 3rd hard-coat layer formation process." The third hard coat layer forming step is, for example, a coating solution for forming a third hard coat layer on the substrate 110 (hereinafter simply referred to as “coating solution” or “third hard coat layer forming material”). There may be.), a coating step of coating the above, and a coating film forming step of drying the applied coating liquid to form a coating film. Moreover, for example, the said 3rd hard-coat layer formation process may contain the hardening process of hardening the said coating film further. The curing may be performed, for example, after drying, but is not limited thereto. The said hardening can be performed by heating, light irradiation, etc., for example. Although the said light is not specifically limited, For example, an ultraviolet-ray etc. may be sufficient. Although the light source of the said light irradiation is also not specifically limited, For example, a high pressure mercury lamp etc. may be sufficient.

The said coating liquid (3rd hard-coat layer forming material) may be a coating liquid containing, for example, a resin material and a dilution solvent (Hereinafter, it may only be called "solvent".). Moreover, the said coating liquid may contain other components other than these, and does not need to contain it. Although it does not specifically limit as said other component, For example, a thixotropy imparting agent, the said nano silica particle, etc. are mentioned. In addition, in FIG. 3, the example in which the 3rd hard-coat layer 103 contains the nano silica particle 103P was shown. However, as mentioned above, the said 3rd hard-coat layer may contain the nano silica particle, and the hard-coat film of this invention does not need to contain it.

The resin material contained in the coating solution may be, for example, the resin itself that forms the third hard coat layer 103, or may be a resin material that forms the resin by polymerization, curing, or the like. Although the said resin is not specifically limited, For example, a thermosetting resin, ionizing-radiation hardening resin, etc. may be sufficient. Moreover, the said resin may contain the acrylate resin (it is also mentioned an acrylic resin), for example, and may contain the urethane acrylate resin, for example. Moreover, the copolymer of curable urethane acrylate resin and polyfunctional acrylate may be sufficient as the said resin, for example.

The said resin material may contain the oligomer and monomer which have a functional group, for example. For example, the resin which forms the 3rd hard-coat layer 103 may be the copolymer of the said monomer and the oligomer which has the said functional group. Although it does not specifically limit as an oligomer which has the said functional group, For example, curable urethane acrylate resin etc. are mentioned. As said curable urethane acrylate resin, the brand name "UV-1700TL" by a Mitsubishi Chemical Co., Ltd. product, "UT-7314" by a Mitsubishi Chemical Co., Ltd. product, etc. are mentioned, for example. Although it does not specifically limit as said monomer, For example, polyfunctional acrylate etc. are mentioned. As said polyfunctional acrylate, the brand name "M-920" by the Toa Synthesis Co., Ltd. product etc. is mentioned, for example.

The said solvent in particular is not restrict|limited, A various solvent can be used and may be used individually by 1 type, and may use 2 or more types together. For example, according to the composition of the said resin, the kind, content, etc. of the said nano silica particle and the said thixotropy imparting agent, you may select an optimal solvent type and solvent ratio suitably. Although it does not specifically limit as said solvent, For example, Alcohol, such as methanol, ethanol, isopropyl alcohol (IPA), a butanol, t-butyl alcohol (TBA), 2-methoxyethanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone; esters such as methyl acetate, ethyl acetate, and butyl acetate; ethers such as diisopropyl ether and propylene glycol monomethyl ether; glycols such as ethylene glycol and propylene glycol; cellosolves such as ethyl cellosolve and butyl cellosolve; aliphatic hydrocarbons such as hexane, heptane, and octane; Aromatic hydrocarbons, such as benzene, toluene, and xylene, etc. are mentioned. Moreover, for example, the said solvent may contain the hydrocarbon solvent and the ketone solvent. The hydrocarbon solvent may be, for example, an aromatic hydrocarbon. The aromatic hydrocarbon may be, for example, at least one selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and benzene. The ketone solvent may be, for example, at least one selected from the group consisting of cyclopentanone and acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, isophorone, and acetophenone. The solvent preferably contains the hydrocarbon solvent (eg toluene) for dissolving the thixotropy-imparting agent (eg, thickener). The solvent may be, for example, a solvent in which the hydrocarbon solvent and the ketone solvent are mixed in a mass ratio of 90:10 to 10:90. The mass ratio of the hydrocarbon solvent and the ketone solvent may be, for example, 80:20 to 20:80, 70:30 to 30:70, or 40:60 to 60:40. In this case, for example, the hydrocarbon solvent may be toluene and the ketone solvent may be methyl ethyl ketone. Moreover, while the said solvent contains toluene, for example, at least selected from the group which consists of ethyl acetate, butyl acetate, IPA, methyl isobutyl ketone, methyl ethyl ketone, methanol, ethanol, and TBA. One may be included.

When, for example, an acrylic film is used as the base material 110 to form an intermediate layer (permeation layer), a good solvent for the acrylic film (acrylic resin) can be preferably used. The solvent may be, for example, a solvent containing a hydrocarbon solvent and a ketone solvent as described above. The hydrocarbon solvent may be, for example, an aromatic hydrocarbon. The aromatic hydrocarbon may be, for example, at least one selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and benzene. The ketone solvent may be, for example, at least one selected from the group consisting of cyclopentanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, isophorone, and acetophenone. The solvent may be, for example, a solvent in which the hydrocarbon solvent and the ketone solvent are mixed in a mass ratio of 90:10 to 10:90. The mass ratio of the hydrocarbon solvent and the ketone solvent may be, for example, 80:20 to 20:80, 70:30 to 30:70, or 40:60 to 60:40. In this case, for example, the hydrocarbon solvent may be toluene and the ketone solvent may be methyl ethyl ketone.

As the base material 110, for example, when triacetyl cellulose (TAC) is used, the solvent is not particularly limited, and for example, ethyl acetate, methyl ethyl ketone, MIBK (methyl isobutyl ketone), Cyclopentanone etc. are mentioned, Only 1 type may be used and multiple types may be used together. In this case, the solvent may be, for example, a mixed solvent of MIBK and cyclopentanone. Although the mixing ratio of MIBK and cyclopentanone is not specifically limited, For example, in mass ratio, 90:10-10:90, 80:20-20:80, 70:30-30:70 may be sufficient.

Moreover, by selecting a solvent suitably, when it contains a thixotropy imparting agent, the thixotropy with respect to an anti-glare hard-coat layer forming material (coating liquid) can be expressed favorably. For example, when using organoclay, toluene and xylene can be preferably used alone or in combination. For example, when using polyolefin oxide, methyl ethyl ketone, ethyl acetate, propylene glycol mono Methyl ether can be preferably used alone or in combination. For example, when using modified urea, butyl acetate and methyl isobutyl ketone can be preferably used alone or in combination.

Various leveling agents can be added to the said 3rd hard-coat layer forming material. As said leveling agent, for the purpose of coating nonuniformity prevention (homogenization of a coating surface), for example, a fluorine-type or silicone-type leveling agent can be used. In the present invention, when antifouling properties are required on the surface of the third hard coat layer, or when a layer containing the other antireflection layer (low refractive index layer) or the interlayer filler is formed on the third hard coat layer, etc. A leveling agent can be appropriately selected.

The compounding quantity of the said leveling agent is 5 weight part or less with respect to 100 weight part of said resin, Preferably it is the range of 0.01-5 weight part.

A pigment, a filler, a dispersing agent, a plasticizer, a ultraviolet absorber, a surfactant, an antifouling agent, an antioxidant, etc. may be added to the said 3rd hard-coat layer forming material as needed in the range which does not impair performance. These additives may be used individually by 1 type, and may be used together 2 or more types.

A conventionally well-known photoinitiator as described in Unexamined-Japanese-Patent No. 2008-88309 can be used for said 3rd hard-coat layer forming material, for example.

As a method of coating the said 3rd hard-coat layer forming material (coating liquid) on the base material 110 to form a coating film, For example, a fountain coat method, a die coat method, a spray coat method, a gravure coat method, and a roll Coating methods, such as a coat method and a bar coat method, can be used.

Next, as described above, the coating film is dried and cured to form a third hard coat layer. The said drying may be made to dry naturally, for example, may be air-dried, and may be heat-dried, and the method combining these may be sufficient as it.

The range of 30-200 degreeC may be sufficient as the drying temperature of the said 3rd hard-coat layer forming material (coating liquid), for example. The drying temperature may be, for example, 40 °C or higher, 50 °C or higher, 60 °C or higher, 70 °C or higher, 80 °C or higher, 90 °C or higher, or 100 °C or higher, 190 °C or lower, 180 °C or lower, 170 °C or lower Below, 160°C or lower, 150°C or lower, 140°C or lower, 135°C or lower, 130°C or lower, 120°C or lower, or 110°C or lower may be sufficient. The drying time is not particularly limited, but may be, for example, 30 seconds or more, 40 seconds or more, 50 seconds or more, or 60 seconds or more, and may be 150 seconds or less, 130 seconds or less, 110 seconds or less, or 90 seconds or less.

Although the means in particular of hardening|curing means of the said coating film is not restrict|limited, Ultraviolet hardening is preferable. The irradiation amount of the energy ray source is preferably 50 to 500 mJ/cm 2 as an accumulated exposure amount at an ultraviolet wavelength of 365 nm. If an irradiation amount is 50 mJ/cm<2> or more, hardening will fully advance easily, and the hardness of the 3rd hard-coat layer formed will become high easily. Moreover, coloring of the 3rd hard-coat layer formed as it is 500 mJ/cm<2> or less can be prevented.

As mentioned above, the laminated body of the base material 110 and the 3rd hard-coat layer 103 shown to Fig.3 (a) can be manufactured.

Next, as shown in FIG.3(b), the protective film 120 is laminated|stacked on the surface (surface opposite to the base material 110) of the 3rd hard-coat layer 103 (protective film lamination|stacking process). This protective film lamination|stacking process is not essential in this invention, and it may be implemented or it is not necessary to implement it. Although the protective film 120 is not specifically limited, For example, a polyethylene film, a polyester film, PET film, etc. may be sufficient, For example, Nitto Denko Co., Ltd. brand name "SPV" series etc. may be sufficient. Moreover, although not shown in figure, for example, you may form an adhesion layer on the surface of the 3rd hard-coat layer 103, and may stick the protective film 120 through the adhesion layer. In addition, you may protect the said adhesive layer surface so that it may not be exposed with the protective film 120. Moreover, the protective film 120 may be peeled off immediately before use of the said adhesion layer, and you may stick the hard-coat film of this invention to a to-be-adhered object with the said adhesion layer. Other members other than the hard coat film of this invention in an image display apparatus may be sufficient as the said to-be-adhered object, for example. The formation method of the said adhesive layer is not specifically limited, Although a general method can be used suitably, For example, it can form by coating etc.

The pressure-sensitive adhesive layer may be, for example, an adhesive layer formed of an adhesive (adhesive composition). In the present invention, the pressure-sensitive adhesive layer may be, for example, a layer in which the protective film 120 can be re-peelable from the third hard-coat layer 103 . Although the thickness of the said adhesive layer is not specifically limited, For example, 5 micrometers or more, 10 micrometers or more, 20 micrometers or more, or 25 micrometers or more may be sufficient, For example, 50 micrometers or less, 40 micrometers or less, 30 micrometers or less , 25 µm or less, or 20 µm or less. Although the said adhesive is not specifically limited, For example, a (meth)acrylic-type polymer etc. are mentioned. These may be dissolved or dispersed in a solvent, for example, in the form of a solution or dispersion, and may be used as the pressure-sensitive adhesive (pressure-sensitive adhesive composition). As said solvent, ethyl acetate etc. are mentioned, for example, Only 1 type may be used and multiple types may be used together. The concentration of the solute or dispersoid (eg, the acrylic polymer) in the solution or dispersion may be, for example, 10% by mass or more, or 15% by mass or more, for example, 60% by mass or less, 50% by mass or less. % or less, 40 mass% or less, or 25 mass% or less may be sufficient. In addition, in this invention, "(meth)acrylic polymer" means the polymer or copolymer of at least 1 type of monomer of (meth)acrylic acid, (meth)acrylic acid ester, and (meth)acrylamide. In addition, in the present invention, (meth)acrylic acid means "at least one of acrylic acid and methacrylic acid", and "(meth)acrylic acid ester" means "at least one of acrylic acid ester and methacrylic acid ester" do. As said (meth)acrylic acid ester, linear or branched alkylester of (meth)acrylic acid, etc. are mentioned, for example. In the linear or branched alkylester of (meth)acrylic acid, the number of carbon atoms in the alkyl group may be, for example, 1 or more, 2 or more, 3 or more, or 4 or more, for example, 18 or less, 16 or less, 14 or more. or less, 12 or less, 10 or less, or 8 or less may be sufficient. The said alkyl group may be substituted by 1 or some substituent, for example, and may not be substituted. As for the said substituent, a hydroxyl group etc. are mentioned, for example, In several cases, it may be same or different. Specific examples of the (meth)acrylic acid ester include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. Moreover, only 1 type may be used for the said adhesive, and may use multiple types together.

Furthermore, as shown in FIG.3(c), the 2nd hard-coat layer 102 is formed on the other surface (surface opposite to the 3rd hard-coat layer 103) of the base material 110 (2nd). hard coat layer forming process). After that, as shown in Fig. 3(d), a first hard coat layer 101 is formed on the surface (surface opposite to the base material 110) of the second hard coat layer 102 (first hard coat layer 101). 1 Hard coat layer forming process). The 2nd hard-coat layer formation process and the 1st hard-coat layer formation process are not specifically limited, For example, the composition of a coating liquid (hard-coat layer formation material), the thickness of a hard-coat layer, etc. are a 2nd hard-coat layer It can implement similarly to the 3rd hard-coat layer formation process mentioned above except setting suitably according to (102) and the 1st hard-coat layer 101. Specifically, for example, while using a coating solution containing nano silica particles, the weight average particle diameter of the nano silica particles is determined in the second hard coat layer 102 and the first hard coat layer 101 . set appropriately. Conditions other than that can also be suitably set according to the 2nd hard-coat layer 102 and the 1st hard-coat layer 101. Moreover, for example, when making the hard coat film of this invention into an anti-glare film (anti-glare hard coat film), you may provide unevenness|corrugation in the surface of the 1st hard-coat layer 101. The method of forming this unevenness|corrugation is also not specifically limited, For example, a general method can be used.

As mentioned above, the hard-coat film of this invention can be manufactured. However, as mentioned above, this manufacturing method is an illustration, and the manufacturing method of the hard coat film of this invention is not limited to this. For example, as mentioned above, the hard coat film of this invention may contain other layers other than the said base material, the said 1st hard-coat layer, the said 2nd hard-coat layer, and the said 3rd hard-coat layer. . For this reason, the manufacturing method of the hard-coat film of this invention may include the process of forming the said other layer further. More specifically, for example, as described above, an antireflection layer may be formed outside the first hard coat layer (on the opposite side to the second hard coat layer). The formation method of the said antireflection layer is also not specifically limited, For example, a general method can be used.

Moreover, the manufacturing method of the hard coat film of this invention can be set as a continuous manufacturing method, for example. Specifically, for example, in the manufacturing method of the hard coat film of this invention, the said base material is elongate, conveying the said base material, said 3rd hard-coat layer formation process, said 2nd hard-coat layer formation process, said The manufacturing method which implements a 1st hard-coat layer formation process and another process continuously as needed may be sufficient. More specifically, for example, the said elongate base material is roll shape, and you may implement the manufacturing method of the hard coat film of this invention, feeding out the said base material from a roll.

[3. hard coat film, optical member and image display device]

The hard coat film of this invention is not specifically limited, For example, as mentioned above, a clear film may be sufficient and an anti-glare film (anti-glare hard coat film) may be sufficient as it.

Although the optical member of this invention is not specifically limited, For example, a polarizing plate may be sufficient. The said polarizing plate is also although it does not specifically limit, For example, the anti-glare film of this invention and a polarizer may be included, and also other component may be included. Each component of the said polarizing plate may be bonded together with an adhesive agent, an adhesive, etc., for example.

The image display device of the present invention is also not particularly limited, and any image display device may be used, and examples thereof include a liquid crystal display device, an organic EL display device, an inorganic EL display device, and a plasma display device.

The structure of the image display apparatus of this invention is not specifically limited, For example, the structure similar to a general image display apparatus may be sufficient. For example, in the case of LCD, optical members, such as a liquid crystal cell and a polarizing plate, and each component parts, such as an illumination system (backlight etc.) if necessary, can be manufactured by assembling suitably, and mounting a drive circuit, etc.

The use of the image display apparatus of this invention is not specifically limited, It can be used for arbitrary uses. Examples of such uses include OA devices such as PC monitors, notebook computers, tablets, smartphones, and photocopiers, mobile phones, watches, digital cameras, portable information terminals (PDAs), and mobile devices such as portable game machines, and video cameras. , televisions, home electric appliances such as microwave ovens, back monitors, car navigation system monitors, in-vehicle equipment such as car audio equipment, display equipment such as information monitors for commercial stores, security equipment such as monitoring monitors, long-term care monitors, Nursing care/medical equipment, such as a medical monitor, smart glasses, a VR apparatus, etc. are mentioned. The image display apparatus of the present invention may be, for example, an image display apparatus having a camera function. In that case, for example, as mentioned above, the transparent layer for camera holes of an image display apparatus may be sufficient as the said transparent layer in the hard coat film of this invention. ADVANTAGE OF THE INVENTION According to this invention, as mentioned above, since a hard coat film can be provided without impairing the transparency of a transparent layer, for example, it is possible to provide an image display apparatus without impairing the image quality of a camera image.

Example

Next, the Example of this invention is demonstrated together with a comparative example. However, the present invention is not limited by the following Examples and Comparative Examples.

In addition, in the following examples and comparative examples, the number of parts of a substance is a mass part (weight part) unless otherwise indicated.

In the following examples and comparative examples, the first hard coat layer forming material, the second hard coat layer forming material, and the third hard coat layer forming material were prepared with the following compositions.

[First Hard Coat Layer Forming Material]

100 parts by mass of a polyfunctional acrylate containing nano silica having a weight average particle diameter of 40 nm (trade name "NC035", manufactured by Arakawa Chemical Industry Co., Ltd.), and 2 parts by mass of a leveling agent (trade name "LE-303", manufactured by Shin-Etsu Chemical Industry Co., Ltd.); It diluted to 35 mass % of solid content concentration using cyclopentanone as a dilution solvent. This was made into the 1st hard-coat layer forming material.

[Second Hard Coat Layer Forming Material]

100 parts by mass of polyfunctional acrylate containing nano silica having a weight average particle diameter of 10 nm (trade name "Opstar Z7540", manufactured by Arakawa Chemical Industry Co., Ltd.), and 2 mass parts of a leveling agent (trade name "LE-303", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) Part was diluted to a solid content concentration of 55 mass% using methyl ethyl ketone as a diluent solvent. This was made into the 2nd hard-coat layer forming material.

[Third hard coat layer forming material (when there is no nano silica particle)]

100 parts by mass of a polyfunctional acrylate (trade name "Viscoat #300", manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 3 parts by mass of a photopolymerization initiator (trade name: "OMNIRAD907", manufactured by BASF) using methyl ethyl ketone as a diluting solvent It diluted to 55 mass % of solid content concentration. This was made into the 3rd hard-coat layer forming material (when there is no nano silica particle).

[Third hard coat layer forming material (when nano silica particles are present)]

As the 3rd hard-coat layer forming material (when there are nano silica particles), the thing similar to the said 2nd hard-coat layer forming material was used.

[Example 1]

By the manufacturing method demonstrated in FIG. 3, the hard coat film was manufactured as follows. First, a TAC substrate (manufactured by Konica Minolta Co., Ltd., trade name “KC8UA”) having a thickness of 80 µm was prepared as a substrate. Next, the said 3rd hard-coat layer forming material (when there is no nano silica particle) was coated on one surface of the said base material, it was made to dry in 60 degreeC oven for 60 second, and the coating film was formed. The coating film was irradiated with an ultraviolet-ray with a wavelength of 365 nm with a high-pressure mercury lamp so that the cumulative irradiation light amount was 300 mJ/cm 2 , and cured to form a third hard coat layer. In addition, in this Example, the said 3rd hard-coat layer forming material (when there is no nano silica particle) was coated so that the thickness of a 3rd hard-coat layer might be set to 5 micrometers. Further, a protective film (manufactured by Toray Corporation, trade name "Doretec-7832C") was affixed on the surface of the formed 3rd hard-coat layer on the opposite side to the said base material.

Next, the said 2nd hard-coat layer forming material was coated on the surface on the opposite side to the said 3rd hard-coat layer formation surface in the said base material, it was made to dry in 60 degreeC oven for 60 second, and the coating film was formed. The coating film was irradiated with the ultraviolet-ray with a wavelength of 365 nm with a high-pressure mercury lamp so that the accumulated irradiation light amount might be 300 mJ/cm<2>, it was made to harden|cure, and the 2nd hard-coat layer was formed. In addition, in a present Example, the said 2nd hard-coat layer forming material was coated so that the thickness of a 2nd hard-coat layer might be set to 10 micrometers.

Moreover, the said 1st hard-coat layer forming material was coated on the surface on the opposite side to the said base material in the formed said 2nd hard-coat layer, it was made to dry for 60 second in 60 degreeC oven, and the coating film was formed. The coating film was irradiated with the ultraviolet-ray with a wavelength of 365 nm with a high-pressure mercury lamp so that the accumulated irradiation light amount might be 300 mJ/cm<2>, it was made to harden|cure, and the 1st hard-coat layer was formed. In addition, in a present Example, the said 1st hard-coat layer forming material was coated so that the thickness of a 1st hard-coat layer might be set to 5 micrometers.

As described above, the hard coat film of the present Example (Example 1) was produced. In addition, in the hard coat film of this Example and each following Example and a comparative example, in the pasting to the glass plate mentioned later, the said protective film was peeled from the said 3rd hard-coat layer.

[Example 2]

The hard coat film of this example (Example 2) was prepared in the same manner as in Example 1 except that the thickness of the second hard coat layer was changed to 20 µm and the thickness of the third hard coat layer was changed to 10 µm. prepared.

[Example 3]

The hard coat film of this example (Example 3) was prepared in the same manner as in Example 1 except that the thickness of the first hard coat layer was changed to 10 µm and the thickness of the third hard coat layer was changed to 10 µm. prepared.

[Example 4]

Same as Example 1 except that the thickness of the first hard coat layer was changed to 10 µm, the thickness of the second hard coat layer was changed to 20 µm, and the thickness of the third hard coat layer was changed to 15 µm A hard coat film of the present Example (Example 4) was prepared.

[Example 5]

A third hard coat layer comprising nano silica particles is formed by using the third hard coat layer forming material (when nano silica particles are present) instead of the third hard coat layer forming material (when nano silica particles are not present) A hard coat film of the present Example (Example 5) was produced in the same manner as in Example 1 except that the first and third hard coat layers were changed to 15 µm in thickness.

[Example 6]

The hard coat film of this example (Example 6) was prepared in the same manner as in Example 5 except that the thickness of the second hard coat layer was changed to 20 µm and the thickness of the third hard coat layer was changed to 25 µm. prepared.

[Comparative Example 1]

The hard coat of this comparative example (comparative example 1) in the same manner as in Example 1 except that the thickness of the first hard coat layer was changed to 20 µm, and the second hard coat layer and the third hard coat layer were not formed. A film was prepared.

[Comparative Example 2]

Except not having formed the 1st hard-coat layer, it carried out similarly to Example 5, and manufactured the hard-coat film of this comparative example (comparative example 2).

[Comparative Example 3]

Except having changed the thickness of the 2nd hard-coat layer and the 3rd hard-coat layer into 20 micrometers, respectively, it carried out similarly to the comparative example 2, and the hard-coat film of this comparative example (comparative example 3) was manufactured.

[Formation of antireflection layer]

On the surface opposite to the base material of the 1st hard-coat layer (However, the 2nd hard-coat layer in the hard-coat layer film of said each Example and comparative example does not have a 1st hard-coat layer), in the following method Thus, an antireflection layer (DRY-AR layer) was formed. First, the Nb target is set in a magnetron sputtering apparatus, reactive sputtering is performed, and on the first hard coat layer (the second hard coat layer when the first hard coat layer is not present), the first Nb ₂ O ₅ layer ( A thickness of 12 nm and a refractive index of 2.34) were formed. Next, the Si target was set in a magnetron sputtering apparatus, reactive sputtering was performed, and a first SiO ₂ layer (thickness 39 nm, refractive index 1.46) was formed on the first Nb ₂ O ₅ layer. Next, a second Nb ₂ O ₅ layer (thickness 119 nm, refractive index 2.34) was formed on the first SiO ₂ layer by the same method as the method for forming the first Nb ₂ O ₅ layer. Further, on the second Nb ₂ O ₅ layer, a second SiO ₂ layer (thickness: 78 nm, refractive index 1.46) was formed in the same manner as in the formation method of the first SiO ₂ layer. In this way, an antireflection layer (DRY-AR layer) was formed in which the Nb ₂ O ₅ layer and the SiO ₂ layer were alternately stacked two by two.

[Measuring method of thickness]

The thickness of each layer of the hard coat film was measured by observing the cross section with TEM (transmission electron microscope).

[Method of measuring pencil hardness]

The measurement of pencil hardness was implemented according to the pencil hardness test of JISK5600-5-4 except having made the load into 750 g weight. Moreover, pencil hardness was measured on the conditions of 3 methods of following (1)-(3) about the hard coat film of each said Example and a comparative example, respectively so that it may mention later. In addition, the thickness of the glass plate of following (1)-(3) was 1.5 mm. Moreover, the 25-micrometer-thick adhesive layer in following (2) was formed using the brand name "CS9821UD" by the Nitto Denko Co., Ltd. product as an adhesive. The adhesive layer with a thickness of 5 micrometers in following (3) was formed using the brand name "Monkey" by the Nitto Denko Co., Ltd. product as an adhesive.

(1) When a glass plate and a 3rd hard-coat layer are bonded together by the 25-micrometer-thick adhesive layer

(2) When a glass plate and a 3rd hard-coat layer are bonded together by the adhesive layer of 5 micrometers in thickness

(3) When the third hard coat layer is directly adhered to the glass plate without forming an adhesive layer

[Measurement and evaluation method of curl]

The hard coat film of each said Example and a comparative example was cut out in the square of one side 15 cm from the center with respect to the width direction of the original fabric, and this was made into the measurement sample. When the measurement sample was cut, the diagonal of the square was made to coincide with the MD direction and the TD direction. In addition, on the surface of a base material, MD direction means the direction parallel to the conveyance direction (longitudinal direction of a base material) of the said base material at the time of hard-coat film manufacture. The TD direction means a direction perpendicular to the MD direction on the surface of the substrate. A rod-shaped weight was placed and pressed on the diagonal line in the MD direction of the measurement sample to measure the maximum height [mm] at which the end of the measurement sample in the TD direction floated, and this was evaluated as the size of the curl in the TD direction. Similarly, a rod-shaped weight was placed and pressed on the diagonal line in the TD direction of the measurement sample to measure the maximum height [mm] at which the end in the MD direction of the measurement sample floated, and this was evaluated as the size of the curl in the MD direction. . The greater the height of the injury, the greater the curl.

[Measurement and evaluation method of adhesion of antireflection layer]

The hard coat film of each Example and Comparative Example in which the antireflection layer was formed was cut into a 5 cm square, and the substrate side was Nitto Denko Co., Ltd. adhesive, trade name "CS9821UD", into a 5 cm square It affixed on the glass plate of thickness 1.5mm, and ultraviolet irradiation was carried out with a metal halide lamp. The irradiation conditions were an environmental temperature of 55°C, an environmental humidity of 45%, a light irradiation solubility of 830 W/m 2 , an irradiation time of 240 h, and a BPT temperature of 85°C. After UV irradiation, 1 to 2 mL of isopropyl alcohol is added dropwise onto the antireflection layer, slid with a cloth applied with a load (trade name "Anticon Gold", manufactured by Contactek), and then the antireflection layer is observed with the naked eye and under a microscope (magnification 100 times). The presence or absence of scratches was confirmed. When a flaw was not seen in the antireflection layer in any of visual observation and microscopic observation, it evaluated as adhesiveness (circle), and when a flaw was seen in at least one, it evaluated as adhesiveness x.

The structure of the hard coat film in each said Example and the comparative example, and the evaluation result of a characteristic are shown to following Table 1 and Table 2. In addition, in following Tables 1 and 2, "HC thickness" shows the thickness of each hard-coat layer. "Glue" shows the adhesion layer used for bonding of a glass plate and a 3rd hard-coat layer. "MD" shows the above-mentioned MD direction, ie, on the surface of a base material, it shows the direction parallel to the conveyance direction (longitudinal direction of a base material) of the said base material at the time of hard coat film manufacture. "TD" represents the above-mentioned TD direction, ie, on the surface of the said base material, shows the direction perpendicular|vertical to the MD direction.

In addition, as shown in following Table 1 and Table 2, as for the hard-coat layer of Examples 1-4, a 3rd hard-coat layer does not contain a nano silica particle, The hard-coat film 100a of Fig.1 (a) has the same configuration as As for the hard-coat layer of Examples 5-6, a 3rd hard-coat layer contains a nano silica particle, and is the structure similar to the hard-coat film 100b of FIG.1(b). In addition, as shown in following Tables 1 and 2, pencil hardness is (1) when a glass plate and the 3rd hard-coat layer are bonded together with a 25-micrometer-thick adhesive layer, (2) a glass plate with a 5-micrometer-thick adhesive layer It measured about 3 methods at the time of sticking a 3rd hard-coat layer together directly, without forming an adhesion layer on (3) a glass plate when a 3rd hard-coat layer is bonded together. Those structures are shown in the sectional drawing of FIG.2(a)-(d). 2(a) and (b) are examples using the hard coat films of Examples 1-4 (the 3rd hard-coat layer 103 does not contain a nano silica particle). Fig.2 (a) is an example in which the 3rd hard-coat layer 103 was closely_contact|adhered to the glass plate 21 directly, without using an adhesive. FIG.2(b) is an example which bonded the 3rd hard-coat layer 103 directly to the glass plate 210 with the adhesive 220. FIG. 2(c) and (d) are examples using the hard coat film of Examples 5-6 (the 3rd hard-coat layer 103 contains the nano silica particle 103P). FIG.2(c) is an example in which the 3rd hard-coat layer 103 was closely_contact|adhered to the glass plate 210 directly, without using an adhesive. FIG. 2( d ) is an example in which the third hard-coat layer 103 is directly bonded to the glass plate 210 with the pressure-sensitive adhesive 220 .

As shown in said Tables 1 and 2, all of the hard coat films of Examples 1-6 have high hardness (pencil hardness), curl is suppressed (in the measurement of a curl, the float of the edge of a hard coat film is 0 mm) ), and the adhesion between the visual side surface and the other layer (DRY-AR layer) was high. In particular, even when the hard coat film of Examples 1-4 in which a 3rd hard-coat layer does not contain a nano silica particle bonded together with a glass plate using a 25-micrometer-thick adhesion layer, hardness (pencil hardness) was high. On the other hand, in the comparative example 1 which does not have a 2nd hard-coat layer and a 3rd hard-coat layer, hardness (pencil hardness) is low, and curling occurs and the hard-coat film has become normal. On the other hand, Comparative Examples 2 and 3 having the second hard coat layer and the third hard coat layer but not having the first hard coat layer had high hardness (pencil hardness) and suppressed curl, but a layer different from the visual recognition side surface The adhesiveness of (DRY-AR layer) was low.

As mentioned above, according to this invention, hardness is high, Curl|Karl is suppressed, and the hard coat film, an optical member, and the image display apparatus with high adhesiveness of the visual recognition side surface and another layer can be provided according to this invention. As mentioned above, the hard coat film of this invention can be used also as a clear film and an anti-glare film (anti-glare hard coat film), and since it can be used for a wide variety of optical members and image display devices, the industry The prize use value is great.

This application claims priority on the basis of Japanese Patent Application No. 2021-059320 for which it applied on March 31, 2021, and takes in all the indications here.

100a, 100b hard coat film
101 first hard coat layer
102 second hard coat layer
103 3rd hard coat layer
101P, 102P, 103P nano silica particles
110 entries
120 protective film
210 glass plate
220 adhesive layer

Claims (8)

a base material, a first hard coat layer, a second hard coat layer, and a third hard coat layer;
The first hard coat layer, the second hard coat layer, the base material, and the third hard coat layer are laminated in this order on the visual side,
The first hard coat layer and the second hard coat layer each contain nano silica particles,
The weight average particle diameter of the said nano-silica particle contained in the said 1st hard-coat layer is larger than the weight average particle diameter of the said nano-silica particle contained in the said 2nd hard-coat layer, The hard-coat film characterized by the above-mentioned. The method of claim 1,
The hard coat film in which the said 3rd hard-coat layer does not contain a nano silica particle. The method of claim 1,
The hard coat film whose thickness of a said 3rd hard-coat layer is smaller than the total thickness of the thickness of a said 1st hard-coat layer, and the thickness of a said 2nd hard-coat layer. The method of claim 1,
The weight average particle diameter of the nano-silica particles contained in the first hard coat layer is 30 to 50 nm,
The hard coat film whose weight average particle diameter of the said nano-silica particle contained in a said 2nd hard-coat layer is 5-30 nm. The method of claim 1,
The hard coat film whose light transmittance in wavelength 550nm of the said whole hard coat film is 90 % or more. The optical member containing the hard coat film in any one of Claims 1-5. 7. The method of claim 6,
The optical member which is a polarizing plate. The optical member containing the hard coat film in any one of Claims 1-5, or the hard coat film in any one of Claims 1-5, or any one of Claims 1-5 The image display apparatus containing the hard coat film of Claim 1 and containing the optical member which is a polarizing plate.

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