KR102361847B1 - Hard coat film with optical adjustment layer for transparent conductive film and transparent conductive film - Google Patents

Abstract

The hard coat film with an optical adjustment layer for transparent conductive films which can obtain sufficient blocking resistance also in the transparent conductive film with a transparent conductive layer and can suppress the fall of visibility is provided.
The hard coat film with an optical adjustment layer is equipped with the transparent base material film which consists of an amorphous polymer, the hard-coat layer laminated|stacked in order on one side of the transparent base film, and the optical adjustment layer on it. The optical adjustment layer contains a plurality of particles, the average particle diameter of the particles is larger than the average film thickness of the optical adjustment layer, and the average particle diameter r1 and the average film thickness d1 are in the relationship of 50 nm≤(r1-d1)≤1900 nm . Arithmetic mean roughness Ra in the specific part of the surface of the optical adjustment layer except the convex part formed with particle|grains exists in the range of 0.3 nm - 20 nm.

Description

Hard coat film with optical adjustment layer for transparent conductive film and transparent conductive film

The present invention relates to a hard coat film with an optical adjustment layer for transparent conductive films using a transparent film as a substrate and a transparent conductive film.

Conventionally, for example, a touch panel of a capacitive type or the like has been widely used as a device capable of inputting information by contacting a display screen such as a smart phone or a tablet terminal. Here, as a transparent conductive film for touch panels, it was common to laminate indium tin oxide (ITO: Indium Tin Oxide) as a transparent conductive layer on a base film by a method such as vapor deposition or sputtering (see, for example, Patent Document 1) ).

And, as the base material of the transparent conductive film, a polyethylene terephthalate film, which is a crystalline polymer film with large birefringence, was used. ), it has been proposed to use an amorphous polymer film having a small birefringence as a base material.

However, although the occurrence of the interference fringes described above was eliminated by the transparent conductive film based on the amorphous polymer film, the amorphous polymer film had a drawback in that the surface of the film was easily damaged compared to the crystalline polymer film. Moreover, since the amorphous polymer film also has a drawback that it is more brittle compared to the crystalline polymer film, there is a problem that the film is wrinkled and cracked when it is brought into close contact with a smooth surface such as a conveying roll during conveyance of the film. Then, the hard-coat film for transparent conductive films which provided the hard-coat layer on the single side|surface or both surfaces of an amorphous polymer film was considered. However, in this case, when a hard coat film was wound up in roll shape, there existed a problem of the blocking that the back surface of the base material of a overlapping hard coat film, a hard coat layer, or hard-coat layers will closely_contact|adhere. Therefore, a hard coat layer containing particles of 1 to 5 μm is provided on the amorphous polymer film, and irregularities are formed on the surface of the hard coat layer and the ITO layer (transparent conductive layer) thereon, etc. -blocking) has been proposed (see, for example, Patent Documents 2 and 3).

Japanese Patent Application Laid-Open No. 7-68690 Japanese Patent Laid-Open No. 2013-107349 Japanese Patent Laid-Open No. 2013-243115

However, when a hard coat layer containing particles having a size of 1 to 5 μm is provided on the amorphous polymer film serving as a base material so that irregularities are formed on the surface of the ITO layer (transparent conductive layer), the hard coat layer or the above Depending on the thickness of the ITO layer (transparent conductive layer) or the like, when the particle size is 1 to 2 μm, there is a fear that the blocking resistance is insufficient, and when the particle size is larger than 2 μm, there is a fear that visibility is reduced.

The present invention provides a hard coat film with an optical adjustment layer for a transparent conductive film that can obtain sufficient blocking resistance even in a transparent conductive film provided with a transparent conductive layer by vapor deposition or sputtering method, and can suppress a decrease in visibility; It exists in providing the transparent conductive film using this hard-coat film with an optical adjustment layer.

The hard coat film with an optical adjustment layer for transparent conductive films which concern on this invention, and a transparent conductive film consist of the following structures in order to achieve the said objective. In other words

The hard coat film with an optical adjustment layer for transparent conductive films according to the present invention comprises a transparent base film made of an amorphous polymer, a hard coat layer laminated sequentially on at least one surface of the transparent base film, and optical adjustment thereon provide a layer Here, the optical adjustment layer contains a plurality of particles, the average particle diameter of the particles is larger than the average film thickness of the optical adjustment layer, and the average particle diameter r1 and the average film thickness d1 are

50nm≤(r1-d1)≤1900nm

is in the relationship of And the arithmetic mean roughness Ra in the specific part of the surface of the said optical adjustment layer except the convex part formed with the said particle|grain exists in the range of 0.3 nm - 20 nm. Here, when the optical adjustment layer consists of a plurality of layers (high refractive index layer + low refractive index layer), the average particle diameter r1 is the average particle diameter of all the particles (particles having an average particle diameter larger than the average film thickness d1), and the average film thickness d1 is both When the particles are put in the layer of and when the particles are put only in the high refractive index layer, it is the overall average film thickness, and when the particles are put in only the low refractive index layer, it is the average film thickness of the low refractive index layer (hereinafter the same).

According to this hard coat film with an optical adjustment layer for transparent conductive films, the optical adjustment layer laminated|stacked on the hard-coat layer contains several particle|grains. And the average particle diameter r1 of the particle|grains contained in the optical adjustment layer is larger than the average film thickness d1 of an optical adjustment layer, The difference exists in the range of 50 nm - 1900 nm. Moreover, arithmetic mean roughness Ra in the specific part of the surface of the optical adjustment layer except the convex part formed with particle|grains is set to 0.3 nm - 20 nm. In this way, the difference between the average particle diameter of the particles contained in the optical adjustment layer and the average film thickness of the optical adjustment layer is 50 nm or more, and the arithmetic mean roughness Ra in the specific portion of the surface of the optical adjustment layer is 0.3 nm or more By setting it as this, sufficient blocking resistance can be acquired also in the transparent conductive film in which the transparent conductive layer was provided on the optical adjustment layer after that by vapor deposition, a sputtering method, etc. Further, the difference between the average particle diameter of the particles contained in the optical adjustment layer and the average film thickness of the optical adjustment layer is set to 1900 nm or less, and the arithmetic mean roughness Ra in the specific portion of the surface of the optical adjustment layer is 20 nm or less, Also in a later transparent conductive film, the fall of visibility can be suppressed.

In addition, the average particle diameter r1 of the particles contained in the optical adjustment layer is in the range of 100 nm to 2000 nm, and the average particle diameter r1 (nm) and the number N (pieces/mm ² ) of the particles are

199.03exp(-0.002r1)≤N≤3676.4exp(-0.002r1)

is in the relationship of Here, the number N of particles refers to the number of particles having a height of 50 nm or more from the surface of the optical adjustment layer (the outermost surface when there are multiple optical adjustment layers) (hereinafter the same).

Moreover, the average film thickness d1 of the said optical adjustment layer, and the average particle diameter r1 of the particle|grains contained in this optical adjustment layer are

(d1/r1)<0.5

is in the relationship of

Moreover, the said hard-coat layer contains several particle|grains, the average particle diameter of these particle|grains is smaller than the average film thickness of the said hard-coat layer, These particle|grains are unevenly distributed on the surface of the said hard-coat layer.

Moreover, the average film thickness d2 of the said hard-coat layer, and the average particle diameter r2 of the particle|grains contained in this hard-coat layer are

(d2/r2)>2

is in the relationship of

Moreover, the curved part side area of the surface of the said optical adjustment layer is 200000 micrometers ² or less per 661780 micrometers< ² >. Here, the curved portion-side area of the surface of the optical adjustment layer refers to the area of the surface of the optical adjustment layer that is at least 3 nm from the average height of the optical adjustment layer in the portion in which the particles contained in the optical adjustment layer do not exist (hereinafter, same).

Moreover, the said hard-coat layer and the said optical adjustment layer are provided in one surface of the said transparent base film, and a protective film may be pasted together so that the outermost layer may be formed in the other surface side of the transparent base film.

Moreover, the said hard-coat layer and the said optical adjustment layer are provided in both surfaces of the said transparent base film, and a protective film may be pasted together so that an outermost layer may be formed in either surface side of the transparent base film.

Moreover, as for the transparent conductive film which concerns on this invention, the transparent conductive layer is formed in the surface of the optical adjustment layer in the said hard coat film with an optical adjustment layer.

According to the hard coat film with an optical adjustment layer for transparent conductive films which concerns on this invention, an optical adjustment layer is made to contain particle|grains, and the average particle diameter of the particle|grains is large with respect to the average film thickness of an optical adjustment layer in the range of 50 nm - 1900 nm and, by setting the arithmetic mean roughness Ra of the surface of the optical adjustment layer to 0.3 nm to 20 nm in a specific portion excluding the convex portions formed by particles, sufficient blocking resistance even in a transparent conductive film provided with a transparent conductive layer thereafter can be obtained, and a decrease in visibility can be suppressed.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram of the hard-coat film with an optical adjustment layer of 1st Embodiment of this invention.
It is a figure which shows the relationship between the average particle diameter of the particle|grains of an optical adjustment layer, and a number similarly.
It is a cross-sectional schematic diagram of the hard-coat film with an optical adjustment layer of 2nd Embodiment of this invention.
It is a cross-sectional schematic diagram of the hard-coat film with an optical adjustment layer of 3rd Embodiment of this invention.
It is a cross-sectional schematic diagram of the hard-coat film with an optical adjustment layer of other embodiment of this invention.
It is a cross-sectional schematic diagram of the hard-coat film with an optical adjustment layer of another embodiment of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing the hard coat film with an optical adjustment layer for transparent conductive films which concern on this invention, and a transparent conductive film is demonstrated based on drawing.

1 and 2 show a first embodiment of the present invention. In the figure, the code|symbol 1 shows the hard-coat film with an optical adjustment layer used for a transparent conductive film. 2 represents a transparent base film. 3 represents a hard coat layer. 4 represents an optical adjustment layer.

The hard coat film 1 with an optical adjustment layer is the transparent base film 2 and the hard-coat layer laminated|stacked in order on at least one surface (one surface in the illustrated embodiment) of the transparent base film 2 ( 3) and an optical adjustment layer 4 thereon.

Here, the optical adjustment layer 4 contains several particle|grains 4a, 4a, and the average particle diameter of these particle|grains 4a, 4a is larger than the average film thickness of the optical adjustment layer 4, The average particle diameter r1 and its average film thickness d1

50nm≤(r1-d1)≤1900nm

is in the relationship of That is, the average particle diameter r1 is 50 nm - 1900 nm larger than the average film thickness d1. And the arithmetic mean roughness Ra in the specific part of the surface of the optical adjustment layer 4 excluding the convex part formed by the said particle|grain 4a contained in the optical adjustment layer 4 is 0.3 nm - 20 nm (more preferably It is in the range of 0.3 nm to 10 nm).

Then, as for a transparent conductive film (not shown), the transparent conductive layer is formed in the surface of the optical adjustment layer 4 in this hard coat film 1 with an optical adjustment layer.

According to this hard coat film 1 with an optical adjustment layer, several particle|grains 4a, 4a are contained in the optical adjustment layer 4 laminated|stacked on the hard-coat layer 3. And the average particle diameter r1 of the particle|grains 4a contained in the optical adjustment layer 4 is larger than the average film thickness d1 of the optical adjustment layer 4, The difference exists in the range of 50 nm - 1900 nm. Moreover, the arithmetic mean roughness Ra in the specific part of the surface of the optical adjustment layer 4 except the convex part formed with the particle|grains 4a is 0.3 nm - the range of 20 nm. The difference between the average particle diameter r1 of the particles 4a contained in the optical adjustment layer 4 and the average film thickness d1 of the optical adjustment layer 4 is 50 nm or more, and the specific portion of the surface of the optical adjustment layer 4 is By making arithmetic mean roughness Ra in 0.3 nm or more, sufficient blocking resistance can be acquired also in the transparent conductive film in which the transparent conductive layer was provided on the optical adjustment layer 4 by vapor deposition, a sputtering method, etc. after that. That is, by two types of convex parts, the convex part formed by the particle|grain 4a, and the convex part 4b which forms the arithmetic mean roughness of a specific part, this hard coat film 1 with an optical adjustment layer as well as Blocking resistance is expressed also in the transparent conductive film after that. Moreover, the difference between the average particle diameter r1 of the particle|grains 4a contained in the optical adjustment layer 4, and the average film thickness d1 of the optical adjustment layer 4 shall be 1900 nm or less, and the said specific part of the surface of the optical adjustment layer 4 By making arithmetic mean roughness Ra in 20 nm or less into a transparent conductive film after that, the fall of visibility can be suppressed.

Thus, the optical adjustment layer 4 is made to contain the particle|grains 4a, and the average particle diameter of the particle|grains 4a is enlarged with respect to the average film thickness of the optical adjustment layer 4 in the range of 50 nm - 1900 nm, and optical adjustment By setting the arithmetic mean roughness Ra in a specific portion of the surface of the layer 4 to 0.3 nm to 20 nm, sufficient blocking resistance can be obtained also in the transparent conductive film provided with the transparent conductive layer thereafter, and the decrease in visibility can be suppressed

Moreover, although the hard coat film 1 with optical adjustment layer for transparent conductive films of this invention can be used suitably as objects for a capacitive touch panel, the use is not limited to the object for said touch panels.

Specifically, the transparent base film 2 is made of an amorphous polymer. As this amorphous polymer, although an amorphous olefin which has an alicyclic structure is preferable, it is not limited to this. Examples of the amorphous olefin include a cycloolefin polymer and a cycloolefin copolymer. Moreover, the material of this transparent base film 2 may be polycarbonate, triacetyl cellulose, polyimide, etc. may be sufficient as it. It is preferable that the thickness of this transparent base film 2 is 10 micrometers - 500 micrometers, More preferably, they are 10 micrometers - 200 micrometers, It is good that they are 20 micrometers - 100 micrometers more preferably. In addition, by performing pretreatment such as physical treatment such as coating of an easily adhesive layer or corona discharge treatment on the surface of the transparent base film 2 in advance, the adhesion with the hard coat layer 3 to be laminated can be improved. have.

The average film thickness of the hard coat layer 3 is preferably in the range of 0.5 µm to 10.0 µm, more preferably in the range of 0.75 µm to 5.0 µm in order to obtain hard coat properties. If the film thickness is less than 0.5 μm, there is a fear that the hardness of the hard coat layer 3 becomes insufficient, and when it exceeds 10.0 μm, cracks enter the hard coat layer 3 or the layer above it, or there is a fear that winding becomes difficult There is also a possibility that optical properties such as transparency may be deteriorated.

Moreover, in order to obtain the convex part 4b of the said specific part of an optical adjustment layer (that is, the said value of the arithmetic mean roughness Ra in a specific part), the surface of the hard-coat layer 3 (namely, the transparent base film 2 It is preferable that arithmetic mean roughness Ra is the range of 2 nm - 20 nm, and, as for the surface opposite to the side with ), it is more preferable that it is 3 nm - 10 nm. If the arithmetic mean roughness Ra of the surface of the hard-coat layer 3 is less than 2 nm, there exists a possibility that arithmetic mean roughness Ra in the said specific part of the optical adjustment layer 4 after that may become less than 0.3 nm, and blocking resistance is lowered Moreover, when arithmetic mean roughness Ra of the surface of the hard-coat layer 3 is larger than 20 nm, there exists a possibility that optical characteristics, such as transparency, may fall.

In the illustrated embodiment, a plurality of particles 3a and 3a are contained in the hard coat layer 3 , and the average particle diameter of the particles 3a and 3a is smaller than the average film thickness of the hard coat layer 3 . And these particle|grains 3a, 3a are unevenly distributed on the surface (namely, the surface opposite to the side with the transparent base film 2) of the hard-coat layer 3). Then, the convex part 4b on the surface of the optical adjustment layer 4 on the hard-coat layer 3 may follow the convex part on the surface by these particle|grains 3a, 3a unevenly distributed on the surface of the hard-coat layer 3, , 4b) are formed, and those projections 4b and 4b are reflected in the value of the arithmetic mean roughness Ra in a specific part of the surface of the optical adjustment layer 4 .

Specifically, the hard coat coating liquid for forming the hard coat layer 3 contains a binder, a plurality of particles 3a and 3a having an average particle diameter smaller than the average film thickness of the hard coat layer 3, and a solvent. . And the hard coat coating liquid is coated on the transparent base film 2, and it is made to dry, and during UV exposure (especially in a drying process), the particle|grains 3a are made to be unevenly distributed on the surface of the hard coat layer 3 . By using this method, the suitable surface roughness of the surface of the hard-coat layer 3 can be obtained uniformly and efficiently.

The hard coat coating liquid is a curable composition which forms the hard-coat layer 3 in detail, It is good to contain the particle|grains 3a and a binder, It is good to harden|cure preferably by ultraviolet-ray. The binder contained in the hard coat coating liquid is not particularly limited, but urethane acrylate may be used to impart flexibility while maintaining scratch resistance. The average particle diameter of the particles 3a contained in the hard coat coating solution is preferably in the range of 50 nm to 500 nm, more preferably in the range of 80 nm to 400 nm, and still more preferably in the range of 120 nm to 400 nm. Therefore, convex portions are formed on the surface by these particles 3a and 3a. If the average particle diameter is less than 50 nm, there is a fear that sufficient projections cannot be formed on the surface, and if the average particle diameter exceeds 500 nm, haze may rise there is Moreover, it is preferable that the average film thickness d2 of the hard-coat layer 3, and the average particle diameter r2 of the particle|grains 3a contained in the hard-coat layer 3 exist in the relationship of (d2/r2)>2, and it is this range It is possible to suppress a rise in haze by setting it as

Although it does not specifically limit as particle|grains 3a, Various inorganic type and organic type particle|grains can be used. As the particles 3a, for example, silica, alumina, titania, acrylic resin, styrene-acrylic copolymer resin, styrene resin, urethane resin, epoxy resin, silicone resin, polyethylene resin, phenol resin, etc. Although there exist particle|grains etc., it is not limited to these, You may combine 2 or more types.

When using organic particle|grains for the particle|grains 3a, in order to obtain particle|grains of a desired average particle diameter, what was synthesize|combined by the emulsion polymerization method using acrylic particle|grains is preferable.

Moreover, when using inorganic particles for the particle|grains 3a, it is preferable to use the silica particle which made the surface free energy small by surface treatment, surfactant, etc. Thus, when the surface free energy becomes small, it becomes easy to make the particle|grains 3a unevenly distributed on the surface of the hard-coat layer 3 .

In addition, the hard coat coating liquid may contain additives such as a dispersant, a leveling agent, an antifoaming agent, a thixotropic agent, an antifouling agent, an antibacterial agent, a flame retardant, an anti-wound agent, and a slip agent, if necessary, within a range that does not affect the performance.

Moreover, you may dilute the hard-coat coating liquid using the organic solvent from a viewpoint, such as adjustment of a film thickness. For example, alcohol-based organic solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGM), and diethylene glycol monobutyl ether, methyl ethyl ketone (MEK), methyl Ketone-based organic solvents such as isobutyl ketone (MIBK), cyclohexanone (anone), and acetone, ester-based organic solvents such as butyl acetate, ethyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, and toluene , an aromatic organic solvent such as xylene, or an amide-based organic solvent such as N-methylpyrrolidone, dimethylacetamide or dimethylformamide may be used. And the organic solvents of these examples may be used individually or in combination of 2 or more types, but it is preferable that the solubility parameter δ is in the range of 8-11, and it is further more that the solubility parameter δ is in the range of 8-10. desirable.

For coating, for example, the reverse gravure coating method, the direct gravure coating method, the die coating method, the bar coating method, the wire bar coating method, the roll coating method, the spin coating method, the dip coating method, the spray coating method, and the knife coating method A coating method such as a method, a kiss coat method, or the like, or various printing methods may be used, but the present invention is not limited thereto.

Regarding the drying step, if drying is too fast, agglomeration and uneven distribution to the surface will become insufficient. C is preferred. The longer the drying time, the better. Considering productivity, it is more preferable to set it to about 10 seconds to 120 seconds.

About a UV exposure process, the aggregate of the particle|grains 3a can be fixed to the side of the surface of the hard-coat layer 3 by irradiating and hardening an ultraviolet-ray to the hard-coat layer 3 after drying. A high-pressure mercury lamp, an electrodeless (microwave type) lamp, a xenon lamp, a metal halide lamp, or any other UV irradiation device can be used for UV irradiation. also be In addition, the irradiation amount of ultraviolet rays is in the range of 50 to 800 mJ/cm ² , preferably in the range of 100 to 300 mJ/cm ² .

The optical adjustment layer 4 relieves the phenomenon that the pattern becomes visible to the eye due to the difference in reflectance between the portion in which the patterned transparent conductive layer is present and the portion in which the patterned transparent conductive layer is not present (that is, the pattern is visible) of the transparent conductive film. It is laminated on the hard coat layer 3 for this purpose. In order to alleviate this pattern visibility, it is good to set the refractive index of the optical adjustment layer 4 between the refractive index of the transparent conductive layer and the refractive index of the hard coat layer 3, and therefore the refractive index of the optical adjustment layer 4 is 1.55 to 1.80. It is preferable to be in the range of Moreover, although the average film thickness of this optical adjustment layer 4 changes with the refractive index of the transparent base film 2, the hard-coat layer 3, and the optical adjustment layer 4, it is the range of 5 nm - 500 nm, and a transparent conductive layer It is preferable to adjust the thickness so that the difference in reflectance between the present portion and the non-existent portion is as small as possible. If the film thickness of the optical adjustment layer 4 is less than 5 nm, there is a fear that the particles 4a may fall off, and if the film thickness is greater than 500 nm, sufficient blocking resistance may not be obtained after the transparent conductive layer or metal layer is formed. have.

It is preferable that it is the range of 100 nm - 2000 nm, as for the average particle diameter of the particle|grains 4a contained in the optical adjustment layer 4, it is more preferable that they are 200 nm - 1500 nm, It is still more preferable that they are 400 nm - 1000 nm. By making the average particle diameter of the particle|grains 4a into this range, even after forming a transparent conductive layer and a metal layer into a film by vapor deposition or sputtering method, sufficient blocking resistance can be provided, and the fall of visibility can be suppressed. If the average particle diameter of the particles 4a is less than 100 nm, there is a fear that sufficient blocking resistance may not be obtained after the transparent conductive layer or metal layer is formed by vapor deposition or sputtering method, and if the average particle diameter of the particles 4a is larger than 2000 nm, visibility This may decrease.

Moreover, it is preferable that the relationship between the average film thickness d1 of the optical adjustment layer 4, and the average particle diameter r1 of the particle|grains 4a contained in this optical adjustment layer 4 shall be (d1/r1)<0.5. By setting it as this range, even if it makes small the average particle diameter r1 of the particle|grains 4a, the convex part of sufficient height can be made. And the average particle diameter of the particle|grains 4a can be adjusted from the film thickness of the optical adjustment layer 4, the film thickness of a transparent conductive layer, and the film thickness of a metal layer.

Here, when (d1/r1) < 0.5, more than half of the particles 4a become convex portions, and there is a risk of the particles 4a falling off due to rubbing or the like, but the convex portions of the specific portion of the optical adjustment layer 4 are The presence of (4b) increases the lubricating activity, and it is possible to prevent the particles 4a from falling off due to rubbing or the like.

The optimal amount of the addition amount of the particles 4a is different depending on the average particle diameter of the particles 4a, and the average particle diameter r1 (nm) and the number N (pieces/mm ² ) of the particles 4a are

199.03exp(-0.002r1)≤N≤3676.4exp(-0.002r1)

It is preferable to have a relationship of (the range of this N is indicated by the diagonal line rising to the right in FIG. 2). and more preferably

It is preferable to have a relationship of 480.48exp(-0.002r1) ? N ? 2277exp(-0.002r1) (the range of N is indicated by the diagonal line falling to the right in FIG. 2).

In addition, when large undulations occur on the surface of the optical adjustment layer 4 in the portion where the particles 4a contained in the optical adjustment layer 4 do not exist, conduction becomes difficult when a conductive film such as ITO is provided. There are cases. Then, the area of the surface of the optical adjustment layer 4 used as the curved side by 3 nm or more from the average height of the optical adjustment layer 4 of the part in which the said particle|grain 4a does not exist (the surface of the optical adjustment layer 4 curved portion) lateral area) is preferably 200000 μm ^{2 or less per 661780 μm 2 ,} and more preferably 150000 μm ² or less. That is, the surface of the optical adjustment layer 4 in the portion where the particles 4a is not present is preferably completely flat for conduction of the transparent conductive film, but since there is a problem of blocking resistance, the convex portion 4b This conflicting problem can be solved.

This optical adjustment layer 4 is obtained by coating the optical adjustment layer coating liquid on the surface of the hard-coat layer 3, drying, and UV exposure. As the optical adjustment layer coating solution, a known ceramic material having an adjusted refractive index (for example, “AICAAITRON Z-816-3L (product name)” manufactured by Aica Kogyo Co., Ltd.) or Toyo "LIODURAS TYZ-A15-S (product name)" manufactured by Toyochem Co., Ltd.) can be used. In order to obtain the high refractive index of 1.55-1.80, you may contain metal oxide particle|grains. The metal oxide particles include, for example, oxides of titanium, zirconium, tin, zinc, silicon, niobium, aluminum, chromium, magnesium, germanium, gallium, antimony, platinum, etc., and particularly, zirconium oxide and titanium oxide are preferable. do. Moreover, you may combine two or more types of these oxides.

As a material of the particle|grains 4a contained in the optical adjustment layer 4, polydispersion and monodispersion of inorganic type, organic type, and well-known particle|grains (For example, Soken Chemical & Engineering Co., Ltd. ) product "MX-80H3wT (product name)") can be used.

If necessary, additives such as a dispersing agent, leveling agent, antifoaming agent, thixotropic agent, antifouling agent, antibacterial agent, flame retardant, wound preventing agent, slip agent and the like may be included in the optical adjustment layer coating solution within a range that does not affect the performance. In particular, it is preferable that the leveling agent adjusts the surface tension lowering ability for the purpose of reducing the area on the curved side of the surface of the optical adjustment layer 4 .

Moreover, you may dilute the optical adjustment layer coating liquid using an organic solvent from a viewpoint, such as adjustment of a film thickness. For example, alcohol-based organic solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGM), diethylene glycol monobutyl ether, methyl ethyl ketone (MEK), Ketone-based organic solvents such as methyl isobutyl ketone (MIBK), cyclohexanone (anone), acetone, and ester-based organic solvents such as butyl acetate, ethyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, An aromatic organic solvent such as toluene or xylene, or an amide-based organic solvent such as N-methylpyrrolidone, dimethylacetamide or dimethylformamide may be used. And although the organic solvent of these examples may be used individually or in combination of 2 or more types, it is preferable that the solubility parameter δ is in the range of 8-11, and it is preferable that δ exists in the range of 8-10. The surface tension of the organic solvent to be used is preferably in the range of 20 to 40 dyne/cm ² , and for the purpose of reducing the area on the curved side of the surface of the optical adjustment layer 4, each concentration in the increase in the concentration of the coating film occurring in the drying process It is preferable to select the organic solvent type of the optical adjustment layer coating solution so that the difference in the surface tension with respect to it is small.

For coating, for example, the reverse gravure method, the direct gravure method, the die coat method, the bar coat method, the wire bar coat method, the roll coat method, the spin coat method, the dip coat method, the spray coat method, the knife coat method, the kiss coat method Although a coating method such as a method and various printing methods can be used, it is not limited to these methods.

About the drying process, it is preferable also from a viewpoint of productivity to carry out for about 10 second - 180 second at the temperature of 50 degreeC - 150 degreeC. If the temperature is within a range that does not affect the performance, the higher the temperature, the lower the viscosity of the coating film surface before curing, and the faster leveling (smoothing), the smaller the area on the curved side of the surface of the optical adjustment layer 4, so it is 80 ° C to 150 ° C. It is more preferable to

About a UV exposure process, a film|membrane can be fixed by irradiating and hardening an ultraviolet-ray to the optical adjustment layer 4 after drying. A high-pressure mercury lamp, an electrodeless (microwave type) lamp, a xenon lamp, a metal halide lamp, or any other UV irradiation device can be used for UV irradiation. also be In addition, the irradiation amount of ultraviolet rays is in the range of 50 to 800 mJ/cm ² , preferably in the range of 100 to 300 mJ/cm ² .

3 shows a second embodiment of the present invention. Although this embodiment differs from 1st Embodiment in that the hard-coat layer is also provided in the other surface of the transparent base film 2, it is the same otherwise, and the same code|symbol is attached|subjected to the same part below, and a different part is mainly used Explain.

This hard coat film 1 with an optical adjustment layer is the other surface of the transparent base film 2 (that is, the surface opposite to the one surface in which the hard-coat layer 3 and the optical adjustment layer 4 are provided) It has a 2nd hard-coat layer (5). A plurality of particles 5a and 5a are contained in the second hard coat layer 5, and the particles 5a and 5a are the surface of the second hard coat layer 5 (that is, the transparent substrate film 2). It is ubiquitous on the side opposite to the side where it is. Thereby, scratch resistance and blocking resistance can be provided not only to one surface of the hard coat film 1 with an optical adjustment layer but to the other surface. For this reason, even if it uses the amorphous polymer film which has the fault that it is brittle and the surface is easily damaged in the transparent base film 2, the hard coat film with an optical adjustment layer which has sufficient hard-coat property and sufficient blocking resistance is obtained. In order not to reduce the visibility here, it is preferable to make the average particle diameter of several particle|grains 5a, 5a smaller than the average film thickness of the 2nd hard-coat layer 5, but lubricity and processability of a film are provided more. For the purpose of making it, you may make the average particle diameter of the particle|grains 5a larger than the average film thickness of the 2nd hard-coat layer 5 as needed.

4 shows a third embodiment of the present invention. Although this embodiment differs from 2nd Embodiment in the point in which a protective film is provided, it is other than that, The same code|symbol is attached|subjected to the same part below, and the different part is mainly demonstrated.

In this hard-coat film 1 with an optical adjustment layer, the hard-coat layer 3 and the optical adjustment layer 4 are provided in one surface of the transparent base film 2, The other of the transparent base film 2 The protective film 6 is pasted together so that the outermost layer may be formed in the surface side. In detail, this hard coat film 1 with an optical adjustment layer uses the hard coat film 1 with an optical adjustment layer of 2nd Embodiment as the hard coat film main body 1a with an optical adjustment layer, and has the optical adjustment layer Protection which consists of the transparent base film 6a for protective films and the adhesive layer 6b on the surface of the 2nd hard-coat layer 5 which is the other surface side of the transparent base film 2 in the hard-coat film main body 1a The film 6 is pasted together using the adhesion layer 6b.

Thus, by providing the protective film 6 in the hard coat film 1 with an optical adjustment layer, even when the transparent base film 2 is very thin, etc., workability|operativity can be made favorable and a contamination etc. can also be prevented.

Although the material which forms the protective film 6 is not specifically limited, From a viewpoint of control of the curl during a heat treatment process and after a heat treatment process, the heat shrinkage rate and coefficient of linear expansion are close to the hard coat film main body 1a with an optical adjustment layer. material is preferred.

In addition, this invention is not limited to embodiment mentioned above, In addition, various changes are possible. For example, the some particle|grains 4a, 4a contained in the optical adjustment layer 4 may not have the same diameter, and may differ as shown in FIG. Moreover, this point is the same also in the particle|grains 3a, 3a contained in the hard-coat layer 3.

Moreover, the optical adjustment layer 4 does not need to be one layer, and it does not matter even if it consists of two or more multilayers, such as a high refractive index layer and a low refractive index layer. In that case, the refractive index of the optical adjustment layer on the hard coat layer 3 side is set to a high refractive index of 1.55 to 1.80, and the refractive index of the optical adjustment layer on the side where the transparent conductive layer is laminated is set to a low refractive index of 1.50 or less suitably. The appearance of the pattern can be alleviated. And although the particle|grains 4a contained in the optical adjustment layer may be contained in any layer and may be contained in multiple layers, it is preferable that it is contained in the optical adjustment layer in the side most distant from the transparent base film 2 .

Moreover, in order to make arithmetic mean roughness Ra in the specific part of the surface of the optical adjustment layer 4 into a predetermined range, the hard-coat layer 3 is made to contain several particle|grains 3a, 3a, and hard-coat layer ( A convex part was provided on the surface of 3) (the surface opposite to the side on which the transparent base film 2 is), and the convex part was reflected on the surface of the optical adjustment layer, but the convex part was formed on the surface of this hard coat layer 3 As a method of providing, instead of using the particles 3a, a method of forming a convex portion by phase separation of two or more kinds of materials or a method of forming a convex portion by embossing may be adopted (Fig. Refer to the convex part 3b shown in 6).

Moreover, although the hard-coat layer 3 and the optical adjustment layer 4 are provided in one surface of the transparent base film 2 in the hard coat film 1 with an optical adjustment layer, both surfaces of the transparent base film 2 The hard-coat layer 3 and the optical adjustment layer 4 may be provided in this. And in this case, a protective film may be pasted together so that an outermost layer may be formed in any one surface side of the transparent base film 2 (after all, in the surface of either optical adjustment layer 4).

Moreover, although the particle|grains 5a are contained in the 2nd hard-coat layer 5 in 2nd and 3rd illustration embodiment, this particle|grain 5a does not need to be contained.

(Example)

Hereinafter, the present invention will be described in more detail by way of Examples.

<Example 1>

As the transparent base film 2, "ZeonorFilm ZF16-100 (product name)" made by Nippon Zeon Corporation was used. After corona-treating one surface of this transparent base film 2, the hard-coat layer 3 was laminated|stacked on the one surface, and the hard-coat film was produced. Furthermore, the optical adjustment layer 4 was laminated|stacked on the surface of the hard-coat layer 3 in a hard-coat film, and the hard-coat film with an optical adjustment layer was produced.

(Preparation of hard coat coating solution (1a))

DIC Corporation "PC16-2291 (product name)", butyl acetate, and methyl ethyl ketone (MEK) were mixed in a dispo cup at the following mixing ratio to prepare a hard coat coating solution (1a).

Formulation of hard coat coating liquid (1a) PC16-2291 butyl acetate MEK weight of 6.25g 1.88g of 1.88g of

(Production of hard coat film (1A))

The hard coat coating solution (1a) was applied to the corona-treated side of the transparent base film (2) using a #5 wire bar, and then dried at a temperature of 80°C for 1.0 minutes, followed by a high-pressure mercury lamp The ultraviolet-ray was irradiated on the conditions of 200 mJ/cm< ² > of light quantity using, and the hard coat film 1A was produced.

(Preparation of optical adjustment layer coating liquid (1b))

"AICAAITRON Z-816-3L (product name)" manufactured by Aica Kogyo Co., Ltd. and Soken Chemical & Engineering Co., Ltd. (Soken Chemical & Engineering Co., Ltd.) "CHEMISNOW MX-80H3wT (product name)" and methyl ethyl ketone (MEK) were mixed at the following compounding ratio, and the optical adjustment layer coating liquid (1b) was adjusted.

Mixing of optical adjustment layer coating liquid (1b) Z-816-3L MX-80H3wT MEK weight 1.78g in 0.20mg out of 8.22g

(Preparation of hard coat film (1B) with optical adjustment layer)

The optical adjustment layer coating liquid 1b is applied to the surface of the hard coat layer 3 of the hard coat film 1A using a wire bar #3, and then dried at a temperature of 80° C. for 1.0 minutes, and then The film was placed in a container provided with a window that transmits ultraviolet rays on the upper surface, and the inside of the container was placed in a nitrogen atmosphere for 3 minutes. Then, ultraviolet-ray was irradiated on the conditions of 200 mJ/cm< ² > of light quantity using the high-pressure mercury-vapor lamp, and the hard coat film 1B with an optical adjustment layer was produced.

<Example 2>

The coating liquid of the optical adjustment layer 4 of Example 1 was changed, and the hard coat film with an optical adjustment layer was produced.

(Preparation of optical adjustment layer coating liquid (2b))

"AICAAITRON Z-816-3L (product name)" manufactured by Aica Kogyo Co., Ltd. and Soken Chemical & Engineering Co., Ltd. (Soken Chemical & Engineering Co., Ltd.) "CHEMISNOW MX-40 (product name)" and methyl ethyl ketone (MEK) were mixed at the following compounding ratio, and the optical adjustment layer coating liquid (2b) was adjusted.

Blending of optical adjustment layer coating liquid (2b) Z-816-3L MX-40 MEK weight 1.78g in 0.25mg of of 8.22g

(Preparation of hard coat film (2B) with optical adjustment layer)

Using the optical adjustment layer coating liquid (2b), other than that, it carried out completely similarly to Example 1, and produced the hard coat film 2B with an optical adjustment layer.

<Example 3>

The coating liquid of the optical adjustment layer 4 of Example 1 was changed, and the hard coat film with an optical adjustment layer was produced.

(Preparation of optical adjustment layer coating liquid (3b))

"AICAAITRON Z-816-3L (product name)" manufactured by Aica Kogyo Co., Ltd. and Soken Chemical & Engineering Co., Ltd. (Soken Chemical & Engineering Co., Ltd.) "CHEMISNOW MX-150 (product name)" and methyl ethyl ketone (MEK) were mixed in the following compounding ratio, and the optical adjustment layer coating liquid (3b) was adjusted.

Blending of optical adjustment layer coating liquid (3b) Z-816-3L MX-150 MEK weight 1.78g in of 0.32mg of 8.22g

(Preparation of hard coat film (3B) with optical adjustment layer)

Except for using the optical adjustment layer coating liquid 3b, it carried out completely similarly to Example 1, and produced the hard coat film 3B with an optical adjustment layer.

<Example 4>

The coating liquid of the hard-coat layer 3 of Example 1 was changed, and the hard-coat film was produced. Furthermore, the optical adjustment layer 4 similar to Example 1 was laminated|stacked on the surface of the hard-coat layer 3 of a hard-coat film, and the hard-coat film with an optical adjustment layer was produced.

(Preparation of hard coat coating solution (4a))

DIC Corporation hard coat products "PC16-2291 (product name)" and "PC16-9081 (product name)", butyl acetate and methyl ethyl ketone (MEK) were mixed in the dispo cup in the following mixing ratio. , the hard coat coating solution (4a) was adjusted.

Formulation of hard coat coating liquid (4a) PC16-2291 PC16-9081 butyl acetate MEK weight 3.12g of 3.12g of 1.88g of 1.88g of

(Production of hard coat film (4A))

Using the hard coat coating liquid 4a, other than that, it carried out completely similarly to preparation of the hard coat film 1A of Example 1, and produced the hard coat film 4A.

(Production of hard coat film 4B with optical adjustment layer)

Using the hard coat film 4A, the optical adjustment layer 4 was laminated|stacked just like Example 1 other than that, and the hard coat film 4B with an optical adjustment layer was produced.

<Example 5>

The coating liquid of the optical adjustment layer 4 of Example 4 was changed, and the hard coat film with an optical adjustment layer was produced.

(Preparation of the hard coat film 5B with an optical adjustment layer)

The optical adjustment layer coating liquid 2b was used, and other than that, it carried out completely similarly to Example 4, and produced the hard coat film 5B with an optical adjustment layer.

<Example 6>

The coating liquid of the optical adjustment layer 4 of Example 4 was changed, and the hard coat film with an optical adjustment layer was produced.

(Preparation of the hard coat film 6B with an optical adjustment layer)

Except for using the optical adjustment layer coating liquid 3b, it carried out completely similarly to Example 4, and produced the hard coat film 6B with an optical adjustment layer.

<Example 7>

The coating liquid of the hard-coat layer 3 of Example 1 was changed, and the hard-coat film was produced. Furthermore, the optical adjustment layer 4 similar to Example 1 was laminated|stacked on the surface of the hard-coat layer 3 of a hard-coat film, and the hard-coat film with an optical adjustment layer was produced.

(Preparation of hard coat coating solution (7a))

"AICAAITRON Z-739L (product name)" manufactured by Aica Kogyo Co., Ltd. and Dow Corning Toray Co., Ltd. in the Dispo Cup. ) agent "8019ADDITIVE (product name)" and methyl isobutyl ketone (MIBK) were mixed in the following compounding ratio, and the hard coat coating liquid (7a) was adjusted.

Formulation of hard coat coating liquid (7a) Z-739L 8019ADDITIVE MIBK weight of 10.36g out of 4.1mg of 4.64g

(Production of hard coat film 7A)

Using the hard coat coating liquid 7a, other than that, it carried out completely similarly to preparation of the hard coat film 1A of Example 1, and produced the hard coat film 7A.

(Preparation of the hard coat film 7B with an optical adjustment layer)

Using the hard coat film 7A, the optical adjustment layer 4 was laminated|stacked like Example 1 completely otherwise, and the hard coat film 7B with an optical adjustment layer was produced.

<Example 8>

On the surface (the other surface) of the transparent base film 2 of the hard coat film 1B with an optical adjustment layer of Example 1, the hard-coat layer 3 and the optical adjustment layer 4 in the same procedure as Example 1 It formed and produced the hard coat film 8B with a double-sided optical adjustment layer.

<Example 9>

The coating liquid of the optical adjustment layer 4 of Example 1 was changed, and the hard coat film with an optical adjustment layer was produced.

(Preparation of optical adjustment layer coating liquid 9b)

"AICAAITRON Z-816-3L (product name)" manufactured by Aica Kogyo Co., Ltd. and Soken Chemical & Engineering Co., Ltd. (Soken Chemical & Engineering Co., Ltd.) "CHEMISNOW MX-80H3wT (product name)" and methyl ethyl ketone (MEK) were mixed at the following compounding ratio, and the optical adjustment layer coating liquid 9b was adjusted.

Mixing of optical adjustment layer coating liquid (9b) Z-816-3L MX-80H3wT MEK weight 1.78g in of 0.07mg of 8.22g

(Preparation of hard coat film 9B with optical adjustment layer)

Except for using the optical adjustment layer coating liquid 9b, it carried out completely similarly to Example 1, and produced the hard coat film 9B with an optical adjustment layer.

<Example 10>

The coating liquid of the optical adjustment layer 4 of Example 1 was changed, and the hard coat film with an optical adjustment layer was produced.

(Preparation of optical adjustment layer coating liquid 10b)

"AICAAITRON Z-816-3L (product name)" manufactured by Aica Kogyo Co., Ltd. and Soken Chemical & Engineering Co., Ltd. (Soken Chemical & Engineering Co., Ltd.) "CHEMISNOW MX-80H3wT (product name)" and methyl ethyl ketone (MEK) were mixed at the following compounding ratio, and the optical adjustment layer coating liquid 10b was adjusted.

Blending of optical adjustment layer coating liquid (10b) Z-816-3L MX-80H3wT MEK weight 1.78g in of 0.44mg of 8.22g

(Preparation of the hard coat film 10B with an optical adjustment layer)

Except for using the optical adjustment layer coating liquid 10b, it carried out completely similarly to Example 1, and produced the hard coat film 10B with an optical adjustment layer.

<Example 11>

The coating liquid of the hard-coat layer 3 of Example 1, and the number of the wire bars were changed, and the hard-coat film was produced. Furthermore, the optical adjustment layer 4 similar to Example 1 was laminated|stacked on the surface of the hard-coat layer 3 of a hard-coat film, and the hard-coat film with an optical adjustment layer was produced.

(Adjustment of the hard coat coating solution 11a)

In a dispo cup, "UT-1147/P55 (product name)" manufactured by Nippon Paint Automotive Coatings Co., Ltd. and butyl acetate and methyl isobutyl ketone (MIBK) were mixed in the following mixing ratio. was mixed to prepare a hard coat coating solution (11a).

Mixing of hard coat coating liquid (11a) UT-1147/P55 butyl acetate MIBK weight of 9.00g 2.25mg of of 0.75g

(Production of hard coat film 11A)

The hard coat coating liquid 11a was used, the wire bar of #7 was used for application of the coating liquid, and otherwise, the hard coat film 11A was prepared in exactly the same manner as in the production of the hard coat film 1A of Example 1. has produced

(Preparation of hard coat film 11B with optical adjustment layer)

Using the hard coat film 11A, the optical adjustment layer 4 was laminated|stacked just like Example 1 other than that, and the hard coat film 11B with an optical adjustment layer was produced.

<Example 12>

The coating liquid of the hard-coat layer 3 of Example 1, and the coating liquid of the optical adjustment layer 4 were changed, and the hard-coat film with an optical adjustment layer was produced.

(Adjustment of hard coat coating solution 12a)

In a dispo cup, "AICAAITRON Z-735-35L (product name)" manufactured by Aica Kogyo Co., Ltd. and propylene glycol monomethyl ether (PGM) were added to the following was mixed at a compounding ratio of to prepare a hard coat coating solution (12a).

Formulation of hard coat coating liquid (12a) Z-735-35L PGM weight of 10.36g of 4.64g

(Production of hard coat film 12A)

Using the hard coat coating liquid 12a, other than that, it carried out completely similarly to preparation of the hard coat film 1A of Example 1, and produced the hard coat film 12A.

(Adjustment of optical adjustment layer coating liquid 12b)

"AICAAITRON Z-816-3L (product name)" made by Aica Kogyo Co., Ltd. and Soken Chemical in a dispo cup & Engineering Co., Ltd. "CHEMISNOW MX-80H3wT (product name)" and propylene glycol monomethyl ether (PGM), manufactured by BYK Japan KK "BYK-UV3570 (product name)" was mixed by the following compounding ratio, and the optical adjustment layer coating liquid 12b was adjusted.

Mixing of optical adjustment layer coating liquid (12b) Z-816-3L pcs. MX-80H3wT PGM BYK-UV3570 weight 1.78g in of 0.44mg of 8.22g out of 9mg

(Production of hard coat film 12B with optical adjustment layer)

Except for using the optical adjustment layer coating liquid 12b, it carried out completely similarly to Example 1, and produced the hard coat film 12B with an optical adjustment layer.

<Example 13>

The coating liquid of the optical adjustment layer 4 of Example 12 was changed, and the hard coat film with an optical adjustment layer was produced.

(Adjustment of optical adjustment layer coating liquid 13b)

“LIODURAS TYZ-A15-S (product name)” manufactured by Toyochem Co., Ltd. and Soken Chemical & Engineering Co., Ltd. Ltd.) "CHEMISNOW MX-80H3wT (product name)" and propylene glycol monomethyl ether (PGM) were mixed at the following compounding ratio, and the optical adjustment layer coating liquid (13b) was adjusted.

Mixing of optical adjustment layer coating liquid (13b) TYZ-A15-S MX-80H3wT PGM weight 1.48g of of 0.55mg of 8.22g

(Preparation of hard coat film 13B with optical adjustment layer)

Except having used the optical adjustment layer coating liquid 13b, it carried out completely similarly to Example 12, and produced the hard coat film 13B with an optical adjustment layer.

<Example 14>

The drying conditions of the optical adjustment layer 4 of Example 13 were changed, and the hard coat film with an optical adjustment layer was produced.

(Preparation of hard coat film 14B with optical adjustment layer)

Except having made the drying temperature after coating of the optical adjustment layer into 100 degreeC, it carried out completely similarly to Example 13, and produced the hard coat film 14B with an optical adjustment layer.

<Example 15>

The drying conditions of the optical adjustment layer 4 of Example 14 were changed, and the hard coat film with an optical adjustment layer was produced.

(Preparation of the hard coat film 15B with an optical adjustment layer)

Except having made the drying temperature after coating of the optical adjustment layer into 130 degreeC, it carried out completely similarly to Example 14, and produced the hard coat film 15B with an optical adjustment layer.

<Example 16>

The coating liquid of the optical adjustment layer 4 of Example 15 was changed, and the hard coat film with an optical adjustment layer was produced.

(Adjustment of optical adjustment layer coating liquid 16b)

"LIODURAS TYZ-A15-S (product name)" manufactured by Toyochem Co., Ltd. and Soken Chemical & Engineering Co., Ltd. Ltd.) "CHEMISNOW MX-80H3wT (product name)" and propylene glycol monomethyl ether (PGM) were mixed in the following compounding ratio, and the optical adjustment layer coating liquid (16b) was adjusted.

Blending of optical adjustment layer coating liquid (16b) TYZ-A15-S MX-80H3wT PGM weight 1.48g of 0.20mg out of 8.22g

(Preparation of the hard coat film 16B with an optical adjustment layer)

Except having used the optical adjustment layer coating liquid 16b, it carried out completely similarly to Example 15, and produced the hard coat film 16B with an optical adjustment layer.

<Comparative Example 1>

The coating liquid of the optical adjustment layer 4 of Example 1 was changed, and the hard coat film with an optical adjustment layer was produced.

(Preparation of optical adjustment layer coating liquid (Xb))

Mix Aica Kogyo Co., Ltd. "AICAAITRON Z-816-3L (product name)" and methyl ethyl ketone (MEK) in the dispo cup at the following mixing ratio, The optical adjustment layer coating liquid (Xb) was adjusted.

Blending of optical adjustment layer coating liquid (Xb) Z-816-3L MEK weight 1.78g in of 8.22g

(Preparation of hard coat film (XB) with optical adjustment layer)

Except for using the optical adjustment layer coating liquid (Xb), it carried out completely similarly to Example 1, and produced the hard coat film (XB) with an optical adjustment layer.

<Example 17>

The ITO target was used for the optical adjustment layer 4 side of the hard coat film 1B with an optical adjustment layer of Example 1, 21 nm sputtering vapor deposition was performed, and the transparent conductive film 17 was produced.

<Example 18>

The ITO target was used for the optical adjustment layer 4 side of the hard coat film 2B with an optical adjustment layer of Example 2, 21 nm sputtering vapor deposition was performed, and the transparent conductive film 18 was produced.

<Example 19>

The ITO target was used for the optical adjustment layer 4 side of the hard coat film 3B with an optical adjustment layer of Example 3, sputtering vapor deposition of 21 nm was performed, and the transparent conductive film 19 was produced.

<Example 20>

The ITO target was used for the optical adjustment layer 4 side of the hard coat film 4B with an optical adjustment layer of Example 4, 21 nm sputtering vapor deposition was performed, and the transparent conductive film 20 was produced.

<Example 21>

The ITO target was used for the optical adjustment layer 4 side of the hard coat film 5B with an optical adjustment layer of Example 5, 21 nm sputtering vapor deposition was performed, and the transparent conductive film 21 was produced.

<Example 22>

The ITO target was used for the optical adjustment layer 4 side of the hard coat film 6B with an optical adjustment layer of Example 6, 21 nm sputtering vapor deposition was performed, and the transparent conductive film 22 was produced.

<Example 23>

Using an ITO target on the optical adjustment layer 4 side of the hard coat film 13B with an optical adjustment layer of Example 13, sputtering deposition of 21 nm was performed, annealing in an oven at 145° C. for 1 hour, and transparent A conductive film 23 was produced.

<Example 24>

Using an ITO target on the optical adjustment layer 4 side of the hard coat film 14B with an optical adjustment layer of Example 14, sputtering deposition of 21 nm is performed, annealing in an oven at 145° C. for 1 hour, and transparent A conductive film 24 was produced.

<Example 25>

Using an ITO target on the optical adjustment layer 4 side of the hard coat film 15B with an optical adjustment layer of Example 15, sputtering deposition of 21 nm is performed, annealing in an oven at 145° C. for 1 hour, and transparent A conductive film 25 was produced.

<Example 26>

An ITO target was used for the optical adjustment layer 4 side of the hard coat film 16B with an optical adjustment layer of Example 16, sputtering deposition of 21 nm was performed, annealing in an oven at 145 degreeC for 1 hour, and transparent A conductive film 26 was produced.

<Example 27>

Using a copper target on the ITO layer side of the transparent conductive film 23 of Example 23, sputtering deposition at 200 nm was performed to prepare a transparent conductive film 27 with a metal layer.

<Example 28>

Using a copper target on the ITO layer side of the transparent conductive film 26 of Example 26, sputtering deposition of 200 nm was performed, and the transparent conductive film 28 with a metal layer was produced.

<Evaluation result of hard coat film with optical adjustment layer>

The evaluation result of the hard coat film with an optical adjustment layer is shown to following Table 15 and Table 16.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 of the optical adjustment layer
Average film thickness d1 [nm] 120 120 120 120 120 120 of particles containing an optical adjustment layer
Average particle size r1 [nm] 800 400 1500 800 400 1500 of particles containing an optical adjustment layer
Number N [pcs/mm ² ] 223 931 75 211 882 93 d1/r1 0.15 0.3 0.08 0.15 0.3 0.08 hard coat layer
Average film thickness d2 [nm] 995 980 1052 1111 1002 920 Hard coat layer-containing particles
Average particle size r2[nm] 250 250 250 250 250 250 d2/r2 3.98 3.92 4.21 4.44 4.01 3.68 of the surface of the optical adjustment layer.
Arithmetic mean roughness Ra[nm] *1 4.55 5.25 4.80 7.89 8.20 7.80 Hz [%] 0.40 0.40 0.70 0.50 0.50 0.70 visibility ○ ○ △ ○ ○ △ coefficient of static friction 0.40 0.40 0.41 0.38 0.39 0.38 blocking resistance ○ ○ ○ ○ ○ ○ particle dropout ○ ○ ○ ○ ○ ○ Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 of the optical adjustment layer
Average film thickness d1 [nm] 120 120 120 120 120 120 of particles containing an optical adjustment layer
Average particle size r1 [nm] 800 800 800 800 800 800 of particles containing an optical adjustment layer
Number N [pcs/mm ² ] 250 198 136 405 220 306 d1/r1 0.15 0.15 0.15 0.15 0.15 0.15 hard coat layer
Average film thickness d2 [nm] 1044 1020 999 976 2112 980 Hard coat layer-containing particles
Average particle size r2[nm] 120 250 250 250 - 120 d2/r2 8.7 4.08 3.99 3.90 - 8.17 of the surface of the optical adjustment layer.
Arithmetic mean roughness Ra[nm] *1 1.80 5.65 6.24 5.75 4.29 0.6 Hz [%] 0.40 1.30 0.35 1.20 1.00 0.90 visibility ○ ○ ○ △ ○ ○ coefficient of static friction 0.47 0.40 0.49 0.38 0.49 0.49 blocking resistance ○ ○ ○ ○ ○ ○ particle dropout ○ ○ ○ ○ ○ ○

Note) *1 The arithmetic mean roughness of the surface of the optical adjustment layer represents the arithmetic mean roughness in the range of 50 µm × 50 µm in a specific portion except for the convex portions by particles contained in the optical adjustment layer in Examples.

Example 13 Example 14 Example 15 Example 16 Comparative Example 1 of the optical adjustment layer
Average film thickness d1 [nm] 90 90 90 90 120 of particles containing an optical adjustment layer
Average particle size r1 [nm] 800 800 800 800 - of particles containing an optical adjustment layer
Number N [pcs/mm ² ] 530 505 520 215 0 d1/r1 0.11 0.11 0.11 0.11 - hard coat layer
Average film thickness d2 [nm] 980 980 980 980 1101 Hard coat layer-containing particles
Average particle size r2[nm] 120 120 120 120 250 d2/r2 8.17 8.17 8.17 8.17 4.40 of the surface of the optical adjustment layer.
Arithmetic mean roughness Ra[nm] *1 1.32 1.35 1.41 1.32 1.56 of the surface of the optical adjustment layer.
Area of curved side [μm ² ] 143146 1024 31405 20123 - Hz [%] 0.90 0.89 0.91 0.45 0.15 visibility △ △ △ ○ ○ coefficient of static friction 0.43 0.41 0.43 0.60 1.21 blocking resistance ○ ○ ○ ○ × particle dropout ○ ○ ○ ○ ○

Note) *1 The arithmetic mean roughness of the surface of the optical adjustment layer represents the arithmetic mean roughness in the range of 50 µm × 50 µm in a specific portion except for the convex portions by particles contained in the optical adjustment layer in Examples. In a comparative example, the arithmetic mean roughness of the range of 50 micrometers x 50 micrometers is shown.

As is clear from Table 15 and Table 16, the hard coat film with an optical adjustment layer in Examples 1-16 is particle|grains ( 4a) is included, and the arithmetic mean roughness Ra of the specific part of the optical adjustment layer 4 is 0.3 nm - 10 nm, Hz (haze) is low, the static friction coefficient is lower than 1, and there is no particle dropout. This hard coat film with an optical adjustment layer has good visibility and can acquire sufficient blocking resistance even when a transparent conductive layer is provided in the surface of an optical adjustment layer.

Moreover, although visibility is favorable also in the hard coat film with an optical adjustment layer of the comparative example 1, particle|grains are not added to the optical adjustment layer 4, but the static friction coefficient is over 1. For this reason, when a transparent conductive layer is provided on the surface, sufficient blocking resistance is not acquired.

<Evaluation result of transparent conductive film>

The evaluation results of the transparent conductive film are shown in Tables 17 and 18 below.

Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 of the optical adjustment layer
Average film thickness d1 [nm] 120 120 120 120 120 120 of particles containing an optical adjustment layer
Average particle size r1 [nm] 800 400 1500 800 400 1500 of particles containing an optical adjustment layer
Number N [pcs/mm ² ] 215 830 75 250 1010 80 d1/r1 0.15 0.3 0.08 0.15 0.3 0.08 hard coat layer
Average film thickness d2 [nm] 995 980 1052 1111 1002 920 Hard coat layer-containing particles
Average particle size r2[nm] 250 250 250 250 250 250 d2/r2 3.98 3.92 4.21 4.44 4.01 3.68 ITO film thickness [nm] 21 21 21 21 21 21 Hz [%] 0.76 0.76 1.09 0.82 0.85 0.86 visibility ○ ○ △ ○ ○ △ coefficient of static friction 0.48 0.36 0.51 0.41 0.45 0.42 blocking resistance ○ ○ ○ ○ ○ ○

Example 23 Example 24 Example 25 Example 26 of the optical adjustment layer
Average film thickness d1 [nm] 90 90 90 90 of particles containing an optical adjustment layer
Average particle size r1 [nm] 800 800 800 800 of particles containing an optical adjustment layer
Number N [pcs/mm ² ] 530 505 520 215 d1/r1 0.11 0.11 0.11 0.11 hard coat layer
Average film thickness d2 [nm] 980 980 980 980 Hard coat layer-containing particles
Average particle size r2[nm] 120 120 120 120 d2/r2 8.17 8.17 8.17 8.17 of the surface of the optical adjustment layer.
Arithmetic mean roughness Ra[nm] *1 1.32 1.35 1.41 1.32 of the surface of the optical adjustment layer.
Area of curved side [μm ² ] 143146 1024 31405 20123 ITO film thickness [nm] 21 21 21 21 Hz [%] 1.20 1.19 1.25 0.80 Electrical resistance [Ω/□] 149 145 141 141 visibility △ △ △ ○ coefficient of static friction 0.40 0.41 0.41 0.52 blocking resistance ○ ○ ○ ○

Note) *1 The arithmetic mean roughness of the surface of the optical adjustment layer represents the arithmetic mean roughness in the range of 50 µm × 50 µm in a specific portion except for the convex portions by particles contained in the optical adjustment layer in Examples.

In Table 17 and Table 18, although the hard coat film with an optical adjustment layer of Examples 1-6 and Examples 13-16 is used for the transparent conductive film in Examples 17-26, Hz (haze) is low, , the coefficient of static friction is low. This transparent conductive film has good visibility and has sufficient blocking resistance even when a transparent conductive layer is attached. Moreover, as for the transparent conductive film in Examples 23-26, the curved part side area of the surface of an optical adjustment layer is 200000 micrometers ^{2 or less per 661780 micrometers 2 ,} and electrical resistance value is also low.

<Evaluation result of transparent conductive film with metal layer>

The evaluation result of the transparent conductive film with a metal layer is shown in following Table 19.

Example 27 Example 28 Average film thickness d1 [nm] of the optical adjustment layer 90 90 Average particle diameter r1 [nm] of particle|grains containing an optical adjustment layer 800 800 Number of particles containing the optical adjustment layer N [pieces/mm ² ] 530 215 d1/r1 0.11 0.11 Average film thickness d2 [nm] of hard coat layer 980 980 Average particle diameter r2 [nm] of hard-coat layer containing particle|grains 120 120 d2/r2 8.17 8.17 Arithmetic mean roughness Ra [nm] *1 of the surface of the optical adjustment layer 1.32 1.32 Area on the curved side of the surface of the optical adjustment layer [μm ² ] 143146 20123 ITO film thickness [nm] 21 21 Copper film thickness [nm] 200 200 coefficient of static friction 0.32 0.38 blocking resistance ○ ○

Note) *1 The arithmetic mean roughness of the surface of the optical adjustment layer represents the arithmetic mean roughness in the range of 50 µm × 50 µm in a specific portion except for the convex portions by particles contained in the optical adjustment layer in Examples.

In Table 19, although the transparent conductive films of Examples 23 and 26 are used for the transparent conductive film with a metal layer in Examples 27-28, even if it attaches the metal layer used as an electrode, it has sufficient blocking resistance.

<Evaluation method>

(Hz)

It measured by the method of JIS-K7136 using "Haze Meter NDH2000 (product name)" manufactured by Nippon Denshoku Industries Co., Ltd.

(Visibility)

When the transmitted light of a three-wavelength fluorescent lamp is observed with the naked eye, the case where the particles are hardly visible is denoted as ○, and the case where the particles can be visually confirmed but each particle is not clearly visible is denoted by Δ, and each particle is The visible case was made into X.

(blocking resistance)

Using "AUTOGRAPH AG-IS MS (AG-1kNIS)" (product name) manufactured by Shimadzu Corporation, a vertical load of 4.4 kg was applied to an area of 60 mm x 50 mm in the friction direction. The coefficient of static friction between the measurement surfaces of the sample was measured. The case where the static friction coefficient was 1 or more was made into x, and the case where it was less than 1 was made into (circle).

(Particle dropout)

Using "AB-301 COLOR FASTNESS RUBBING TESTER (product name)" manufactured by Tester Sangyo Co., Ltd., flannel (No. 16 twin yarn flannel WKF2254) was applied to 500 reciprocating optical adjustment layers under a load of 500 g. The surface was rubbed, and after that, it was confirmed whether the particle|grains 4a did not fall off using "Microscope VHX-1000 (product name)" manufactured by Keyence Corporation on the surface. The thing without drop-off|omission of the particle|grains 4a was made into (circle), and the thing with drop-off|omission of the particle|grain 4a was made into x.

(average thickness of hard coat layer)

The average film thickness of the hard-coat layer 3 was measured using "Filmetrics F20 film thickness measurement system (product name)" made by Filmetrics Corporation.

(Average film thickness of optical adjustment layer)

The film thickness of the optical adjustment layer 4 was measured in the following procedure.

(1) Using "UV3600 (product name)" by Shimadzu Corporation, the reflectance in wavelength 380-800 nm is measured, and a waveform is obtained.

(2) information on the laminated film other than the film thickness of the optical adjustment layer 4 in the optical simulation software [configuration, refractive index (1.52) of the transparent base film 2) and thickness, 1.50), the average film thickness (measured value of the average film thickness of the hard coat layer 3 described above), and the refractive index of the optical adjustment layer (Examples 13-16 were set to 1.60. Other examples were set to 1.62) )] is inserted.

(3) Let the film thickness value when the waveform obtained by inputting arbitrary film thicknesses into the optical adjustment layer of optical simulation match with the waveform obtained in (1) be the average film thickness of an optical adjustment layer.

That is, after obtaining an interference waveform using "UV3600 (product name)" manufactured by Shimadzu Corporation, the film thickness value at which the measured interference waveform and the calculated waveform by simulation coincide with the value of the optical adjustment layer It was set as the average film thickness.

(Average particle diameter of the particles contained in the hard coat layer)

The arithmetic mean value of the volume-based particle diameter distribution obtained by the laser diffraction/scattering method according to the Japanese industrial standard JIS Z8825 based on the international standardization organization standard ISO 13320 was taken as the average particle diameter of the particles.

(Average particle diameter of particles contained in the optical adjustment layer)

The arithmetic mean value of the volume-based particle diameter distribution obtained by the laser diffraction/scattering method according to the Japanese industrial standard JIS Z8825 based on the international standardization organization standard ISO 13320 was taken as the average particle diameter of the particles.

(arithmetic mean roughness Ra of a specific part of the optical adjustment layer)

Mitsubishi Chemical Systems, Inc. (former name: Ryoka Systems Inc.) “Non-contact surface/layer cross-section shape measurement system VertScan 2.0 (model: R5300GL-L-A100)” -AC) (product name)", the sample cut out to 50 mm x 50 mm was placed on the stage, and the surface shape was measured with a 10x lens. Then, the measurement data was observed and the arithmetic mean roughness Ra of the range of 50 micrometers x 50 micrometers was computed in the specific part except the convex part formed by the particle|grains 4a contained in the optical adjustment layer 4.

(Number of particles containing the optical adjustment layer)

Mitsubishi Chemical Systems, Inc. (former name: Ryoka Systems Inc.) “Non-contact surface/layer cross-section shape measurement system VertScan 2.0 (model: R5300GL-L-A100)” Using -AC (product name)), the sample cut out to 50 mm x 50 mm was placed on the stage, and the surface shape was measured with a 10x lens. Then, particle analysis of the measurement data was performed, and the number of particles with a height of 50 nm or more was counted from the surface of the optical adjustment layer 4 in 1 mm x 1 mm.

(Area on the curved side of the surface of the optical adjustment layer)

Mitsubishi Chemical Systems, Inc. (former name: Ryoka Systems Inc.) “Non-contact surface/layer cross-section shape measurement system VertScan 2.0 (model: R5300GL-L-A100)” -AC (product name))", the sample cut out to 50 mm x 50 mm was placed on the stage, and the surface shape was measured with a 5x lens. Thereafter, bearing analysis of the measurement data is performed, and the area on the curved side by 3 nm or more from the average height of the optical adjustment layer 4 in the portion where the particles 4a do not exist (the surface of the optical adjustment layer on the curved side area) was calculated as a value per 661780 µm ² .

(Electrical resistance value of transparent conductive film)

"Loresta-GP (model: MCP-T610) (product name)" manufactured by Mitsubishi Chemical Analytech Co., Ltd. (formerly known as Mitsubishi Chemical Analytech) is used. was measured.

(Industrial Applicability)

The hard coat film and transparent conductive film with an optical adjustment layer shown above are used suitably for a capacitive touchscreen etc.

One… Hard coat film with optical adjustment layer
2… transparent base film
3… hard coat layer
3a… particle
4… optical adjustment layer
4a… particle
6… protective film

Claims (10)

A hard coat with an optical adjustment layer for a transparent conductive film comprising a transparent base film made of an amorphous polymer, a hard coat layer laminated on at least one surface of the transparent base film, and an optical adjustment layer laminated on the hard coat layer As a film,
The optical adjustment layer contains a plurality of particles forming convex portions on the surface of the optical adjustment layer, the average particle diameter of these particles is larger than the average film thickness of the optical adjustment layer, the average particle diameter r1 and the average film thickness d1 this
50nm≤(r1-d1)≤1900nm
is in the relationship of
Arithmetic mean roughness Ra in a specific part of the surface of the said optical adjustment layer except the convex part formed by the said particle|grains exists in the range of 0.3 nm - 20 nm, and
The hard coat film with an optical adjustment layer for transparent conductive films in which average particle diameter r1 of the said particle|grains contained in the said optical adjustment layer exists in the range of 100 nm - 2000 nm. The method according to claim 1, wherein the average particle diameter r1 (nm) of the particles contained in the optical adjustment layer and the number N (pieces/mm ² ) of the particles are
199.03exp(-0.002r1)≤N≤3676.4exp(-0.002r1)
The hard coat film with an optical adjustment layer for transparent conductive films characterized by the above-mentioned relationship. The average film thickness d1 of the said optical adjustment layer, and the average particle diameter r1 of the said particle|grains contained in this optical adjustment layer according to Claim 1 or 2
(d1/r1)<0.5
The hard coat film with an optical adjustment layer for transparent conductive films characterized by the above-mentioned relationship. 3. The hard coat layer according to claim 1 or 2, wherein the hard coat layer contains a plurality of particles, the average particle diameter of the particles is smaller than the average film thickness of the hard coat layer, and the particles are deposited on the surface of the hard coat layer. It is unevenly distributed, The hard coat film with optical adjustment layer for transparent conductive films characterized by the above-mentioned. The average film thickness d2 of the said hard-coat layer and the average particle diameter r2 of the particle|grains contained in the said hard-coat layer according to claim 4,
(d2/r2)>2
The hard coat film with an optical adjustment layer for transparent conductive films characterized by the above-mentioned relationship. The curved part side area of the surface of the said optical adjustment layer is 200000 micrometers ^{2 or less per 661780 micrometers 2 The} hard coat film with optical adjustment layers for transparent conductive films of Claim 1 or 2 characterized by the above-mentioned. The said hard-coat layer and the said optical adjustment layer are provided in one surface of the said transparent base film, and a protective film is pasted together so that an outermost layer may be formed in the other surface side of this transparent base film. A hard coat film with an optical adjustment layer for transparent conductive films, characterized in that. The hard coat layer is provided on the other surface of the said transparent base film, and the said protective film is pasted together on the surface of the hard coat layer, The hard-coat with optical adjustment layer for transparent conductive films of Claim 7 characterized by the above-mentioned. coat film. The protective film according to claim 1 or 2, wherein the hard coat layer and the optical adjustment layer are provided on both sides of the transparent base film, and an outermost layer is formed on either side of the transparent base film. It is pasted together, The hard coat film with optical adjustment layer for transparent conductive films characterized by the above-mentioned. The transparent conductive film in which the transparent conductive layer is formed in the surface of the optical adjustment layer in the hard coat film with an optical adjustment layer of Claim 1 or 2.

Images