JPH11258405A - Anti-reflection film - Google Patents

Abstract

(57) [Problem] To obtain an antireflection film in which the surface is hardly damaged by abrasion and the antireflection layer does not peel off. When the antireflection film has an electromagnetic wave shielding function, the electromagnetic wave shielding effect is maintained for a long time. SOLUTION: In an antireflection film 10A having an antireflection layer 2 on at least one surface on a film substrate 1,
A water-repellent and / or oil-repellent antifouling layer 3 is formed on the uppermost layer of the antireflection layer 2, and the surface of the antifouling layer 3 has a dynamic friction coefficient of 0.3 or less. Alternatively, the top layer of the antireflection layer 2 has a water-repellent and / or oil repellency, dynamic friction coefficient of the surface is 0.3 or less of the low refractive index layer 2b _3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antireflection film applied to a surface such as a display screen of a display. More specifically, the present invention relates to an anti-reflection film in which the surface of the anti-reflection layer is hardly damaged and the anti-reflection layer is prevented from peeling off, and further relates to such an anti-reflection film having an electromagnetic wave shielding function.

[0002]

2. Description of the Related Art Conventionally, many displays are used in an environment where external light or the like is incident both indoors and outdoors. External light that has entered the display is specularly reflected on the display surface or the like, and the reflected image mixes with the original display light of the display to reduce the display quality, making it difficult to view the display image.

In particular, with the recent shift to office automation in offices, the frequency of using computers has increased, and CRTs and LCDs have been increasingly used.
(Liquid crystal display) has become longer. For this reason, a decrease in display quality due to a reflected image of external light or the like is considered to be a factor that causes health disorders such as eye fatigue, and it is required to reduce unnecessary external light reflection.

Further, in recent years, with the spread of outdoor life, the chances of using displays such as CRTs and LCDs outdoors tend to increase more and more, and the display quality is further improved so that the displayed images can be clearly recognized. There is also a demand for it.

[0005] As an example of satisfying these requirements,
It is known to bond an antireflection film having an antireflection effect over a wide range of visible light to a surface of a display or the like. As such an antireflection film,
On the surface of a film substrate made of transparent plastic, an antireflection layer having a laminated structure of a high refractive index layer and a low refractive index layer made of metal oxide or the like formed via a hard coat layer, or an antireflection layer A single layer of a low refractive index layer made of silicon oxide, an organic fluorine compound, or the like is used.

[0006] Separately, a coating layer containing transparent fine particles is formed on the surface of a film substrate made of transparent plastic, and external light is irregularly reflected on the uneven surface, thereby providing the same antireflection film as that described above. It is known that an effect can be obtained.

[0007] On the other hand, in recent years, there is a tendency to require an electromagnetic wave shielding function for a film attached to the surface of a display. By attaching a film having an electromagnetic wave shielding function to the front surface of the display, static electricity can be eliminated, dust can be prevented from adhering, and the displayed image can be easily viewed. More recently, as mobile communication networks represented by mobile phones continue to expand, the effect of emitted electromagnetic waves on displays has been viewed as a problem. For example, in a CRT, an LCD, a PDP (Plasma Display Panel), and the like, external electromagnetic waves other than the electromagnetic waves emitted by the display itself become noise to the display. Therefore, it is required that the antireflection film has an electromagnetic wave shielding function.

When an anti-reflection film is provided with an electromagnetic wave shielding function, it is most common to form a conductive layer on the anti-reflection film using a thin metal or transparent conductive ceramic and ground the conductive layer. . In this case, the conductive layer is formed in the anti-reflection layer of the anti-reflection film, or formed solely on the reflection surface of the film substrate on which the anti-reflection layer is formed.

[0009]

However, in the conventional antireflection film, the surface of the antireflection layer is easily damaged by abrasion. Therefore, even if the anti-reflection film is attached to the surface of the display, the display image becomes difficult to recognize due to the scratches formed on the surface of the anti-reflection layer, the appearance is significantly deteriorated, and the scratches are used as a trigger. Problems such as peeling of the antireflection layer occur. In the antireflection film having an electromagnetic wave shielding function,
There are problems such as deterioration of the electromagnetic wave shielding function.

The present invention has been made in view of such problems, and it is an object of the present invention to prevent the surface of the antireflection layer from being easily scratched by abrasion and preventing the antireflection layer from peeling off. It is to provide a film. Another object of the present invention is to provide an anti-reflection film in which the anti-reflection film has an electromagnetic wave shielding function when the anti-reflection film has an electromagnetic wave shielding function for a long period of time.

[0011]

Means for Solving the Problems In order to achieve the above object, the present inventor has proposed an antireflection film having an antireflection layer on at least one surface of a film substrate. An antireflection film, wherein an antifouling layer having water repellency and / or oil repellency is formed, and the dynamic friction coefficient of the surface of the antifouling layer is 0.3 or less, preferably 0.2 or less. I will provide a.

Further, in an antireflection film having an antireflection layer on at least one surface of a film substrate, the uppermost layer of the antireflection layer comprises a low refractive index layer having water repellency and / or oil repellency, Provided is an antireflection film, wherein the coefficient of dynamic friction of the surface of the refractive index layer is 0.3 or less, preferably 0.2 or less.

Further, in the above antireflection film,
An embodiment is provided in which the antireflection layer includes a conductive layer.

Further, the present invention provides a display device comprising an optical functional film having the above-mentioned antireflection film on the surface and a display having the above antireflection film on the surface.

According to the antireflection film of the present invention, an antireflection film comprising a film substrate and an antireflection layer has an antifouling layer having water repellency and / or oil repellency on the uppermost layer of the antireflection layer. Alternatively, since the low refractive index layer itself as the uppermost layer of the antireflection layer has water repellency and / or oil repellency, the antifouling property of the antireflection film surface is improved. Furthermore,
The layer having water repellency and / or oil repellency has a dynamic friction coefficient of 0.3 or less, preferably 0.2 or less, and thus has a surface with good slipperiness and improved scratch resistance.

In particular, in the antireflection film of the present invention, when the antireflection layer includes a conductive layer, the antireflection film has a high antifouling property and also has an electromagnetic wave shielding function.

Further, by bonding the antireflection film of the present invention to another optical functional film such as a deflecting film or a display of a display device, the optical functional film or the display is similarly provided with antifouling property. be able to. Therefore, a display device having such a display is less likely to be scratched by the abrasion on the display, easily recognizes a displayed image for a long time, and has an electromagnetic wave shielding effect.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below in detail with reference to the drawings. In each of the drawings, the same reference numerals represent the same or equivalent components.

FIG. 1 shows an antireflection film 10A in which an antireflection layer 2 and an antifouling layer 3 are formed on one surface of a film substrate 1. The antireflection layer 2 is made of a high refractive index layer 2a.
And a low-refractive-index layer 2b are alternately laminated, and have a laminated structure of a total of four layers, and a layer configuration diagram in which a hard coat layer 4 is formed between the film substrate 1 and the antireflection layer 2 It is.

In the anti-reflection film 10A, a smooth and transparent plastic film can be used as the film substrate 1. For example, polymethyl methacrylate, polycarbonate, polystyrene,
Polyethylene sulfide, polyether sulfone, polyolefin, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose and the like can be used, and are appropriately selected depending on the purpose and use. The thickness of the film substrate 1 is selected and set depending on the type, purpose, and use of the plastic film constituting the film substrate.
A thickness of 0 to 200 μm is preferred.

The anti-reflection layer 2 utilizes the coherence of light, and is generally composed of a layer having a predetermined optical thickness nd (refractive index n × shape thickness d) in order to obtain desired anti-reflection characteristics. However, the antireflection layer 2 of the antireflection film 10A of FIG.
The high refractive index layer 2a and the low refractive index layer 2b are alternately arranged, and a total of four layers are laminated so that the low refractive index layer 2b is located on the uppermost layer.

As described above, the antireflection layer 2 is formed of the high refractive index layer 2a.
FIG. 1 shows a case where the number of layers is four, and the number of layers is not limited to four in the present invention. Usually, it is preferable to use 2 to 6 layers from the viewpoint of cost and antireflection effect.

Here, from the viewpoint of obtaining a practical antireflection effect, the high refractive index layer 2a preferably has a refractive index n _H = 1.8 or more, more preferably 1.95 or more. The low refractive index layer 2b preferably has a refractive index n _L = 1.6 or less, more preferably 1.5 or less.

As a material for forming such a high refractive index layer 2a, practically, titanium oxide, zirconium oxide, tantalum oxide, zinc oxide, indium oxide, hafnium oxide, cerium oxide, tin oxide, niobium oxide , Yttrium oxide, ytterbium oxide, metal oxides such as indium tin oxide, or a mixture containing these as main materials can be used.

The method for forming the high refractive index layer 2a includes a vacuum deposition method, a reactive deposition method, an ion beam assisted deposition method,
Sputtering, ion plating, and vacuum deposition processes such as plasma CVD can be used.
Any film forming method may be used.

On the other hand, as a material for forming the low refractive index layer 2b, inorganic compounds such as silicon oxide, magnesium fluoride, calcium fluoride and barium fluoride can be used. Further, an organic silicon resin, an organic resin containing a polyfunctional group such as an acrylic resin, a urethane resin, a polyester resin, or a melamine resin can also be used.

When the inorganic compound layer is formed, the low refractive index layer 2b can be formed by a vacuum film forming process as in the case of the high refractive index layer 2a. When forming an organic resin layer, a film forming process combining a wet coat such as a gravure coat or a screen coat with a heat drying method, a heat curing method, an ultraviolet irradiation curing method, an electron beam irradiation curing method, or the like may be used. A method optimal for the properties of each organic resin such as coatability and curability is appropriately selected. Any other film forming method may be used. In the case of the ultraviolet curing method, the electron beam irradiation curing method, or the like, the organic resin is heated and vaporized in a vacuum or mist is introduced by ultrasonic waves, and the mist is introduced and irradiated near the base material to form the low refractive index layer 2b. It is also possible.

The antifouling layer 3 is characteristic of the present invention in that it has water repellency and / or oil repellency and has a dynamic friction coefficient of 0.3 or less on its surface. The anti-reflection layer 2 has a low surface reflectance, so that dirt and scratches are conspicuous, but the anti-reflection layer 2 is provided with a water-repellent and / or oil-repellent anti-fouling layer 3 to protect the surface of the anti-reflection layer 2, and By providing antifouling property, more specifically, by providing the water-repellent antifouling layer 3, it is possible to repel water and make it difficult to adhere dirt, and to provide the oil-repellent antifouling layer 3. This makes it possible to easily wipe off dirt such as oil-based ink and fingerprints.

Various organic compounds can be used as a material for forming the antifouling layer 3 depending on the degree of water repellency or oil repellency imparted to the antifouling layer 3. As a preferable forming material exhibiting oil repellency, a fluorine-containing organic compound can be given. Among them, those exhibiting water repellency include, for example, fluorocarbon, perfluorosilane, and polymer compounds thereof. In addition, a polymer compound having an oil-repellent group such as a methyl group is suitable for improving fingerprint wiping properties and the like.

The antifouling layer 3 can be formed by a vacuum deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a plasma polymerization method, a microgravure method, Various wet process coating methods such as a screen coating method and a dip coating method can be used.

As a method for controlling the dynamic friction coefficient of the surface of the antifouling layer 3 to 0.3 or less, preferably 0.2 or less, the layer may be formed so as to have a uniform and uniform surface. In addition,
When the antifouling layer 3 is formed by the above forming method using the above forming material, the above forming material is inherently low in surface energy and easily obtains a surface having a low dynamic friction coefficient. , The dynamic friction coefficient can be reduced to 0.3 or less.

It is necessary to set the thickness of the antifouling layer 3 so as not to impair the function of the antireflection layer 2, and it is usually preferable that the thickness of the antifouling layer 3 be 50 nm or less, more preferably 10 nm or less.

The hard coat layer 4 formed between the film substrate 1 and the anti-reflection layer 2 prevents the anti-reflection layer 2 from being scratched by the load of a pencil or the like, and causes cracks due to bending of the film. Such as suppressing things
In order to improve the mechanical strength of the antireflection film 10A,
It is provided as needed in the present invention.

The material for forming the hard coat layer 4 is not particularly limited as long as it has transparency, appropriate hardness and mechanical strength. For example, a resin that can be cured by irradiation with an electron beam or an ultraviolet ray, a thermosetting resin, or the like can be used. In particular, an ultraviolet irradiation-curable acrylic resin, an organic silicon-based resin, and a thermosetting polysiloxane resin are preferable. More preferably, these resins have the same or similar refractive index as the film substrate 1.

Although the thickness of the hard coat layer 4 depends on the resin to be formed, it is usually sufficient if the thickness is 3 μm or more. From the viewpoint of transparency, coating accuracy, and handleability, the thickness is preferably 5 to 7 μm.

In the hard coat layer 4, transparent inorganic or organic ultrafine particles having an average particle diameter of 0.01 to 3 μm may be mixed and dispersed. You may. By using such ultrafine particles, a light diffusing treatment generally called anti-glare can be performed. The material for forming these ultrafine particles is not particularly limited as long as it is transparent, but a low refractive index material is preferable, and inorganic silicon oxide and magnesium fluoride are particularly preferable in terms of stability, heat resistance, and the like. Further, as a method for forming the hard coat layer 4, any coating method can be used as long as the coating is performed uniformly.

FIG. 2 is a layer configuration diagram of an antireflection film 10B according to another embodiment of the present invention. This antireflection film 1
0B is an anti-reflection layer 2 in which a hard coat layer 4, a high-refractive index layer 2a and a low-refractive index layer 2b are alternately laminated on one surface of a film substrate 1, similarly to the anti-reflection film 10A of FIG. , And the antifouling layer 3, wherein one of the upper layers of the high refractive index layer 2 a constituting the antireflection layer 2 is a conductive layer X.

By providing the conductive layer X in the anti-reflection layer 2 as described above, it is possible to impart an electromagnetic wave shielding function to the anti-reflection film 10B. This conductive layer X
Is a high-refractive-index layer 2a constituting the anti-reflection layer 2, and therefore, a material having a high refractive index and exhibiting conductivity is used as a material for forming the conductive layer X. For example, a simple substance of zinc oxide, indium oxide, tin oxide, or a mixture thereof can be used. The conductive layer X may be mixed with a metal such as aluminum, zinc, indium, and tin as a dopant. Thereby, the resistance value can be adjusted and the resistance can be reduced, and the electromagnetic wave shielding function can be given a wide range.

FIG. 2 shows a high refractive index layer 2 a and a low refractive index layer 2.
b and the antireflection layer 2 in which a total of four layers are alternately laminated, an example is shown in which only one of the upper high-refractive-index layers 2a is the conductive layer X. The mode of forming the layer is not limited to this. For example, in the antireflection film 10B of FIG.
Instead of a, the lower high refractive index layer 2a may be a conductive layer, or both of the two high refractive index layers 2a may be conductive layers. In addition, as long as the antireflection property is not impaired, a conductive layer can be provided at any position of the antireflection layer having any layer configuration.

FIG. 3 is a layer configuration diagram of an antireflection film 10C according to another embodiment of the present invention. This antireflection film 1
0C has a hard coat layer 4 on one side of the film substrate 1.
The antireflection layer 2 and the antifouling layer 3 are formed in the same manner as the antireflection film 10A of FIG. 1 described above.
c, in that it has a layer configuration in which a high refractive index layer 2a and a low refractive index layer 2b are sequentially laminated. When the antireflection layer 2 is composed of the three layers of the intermediate refractive index layer 2c, the high refractive index layer 2a, and the low refractive index layer 2b, the high refractive index layer 2a and the low refractive index layer 2b correspond to the above-described figures. 1 high refractive index layer 2a and low refractive index layer 2b,
The intermediate refractive index layer 2c includes a high refractive index layer 2a and a low refractive index layer 2b.
The material is appropriately selected and formed so as to have an intermediate refractive index of the above. Preferably, the refractive index of the high refractive index layer 2a is 1.
8 and the refractive index of the intermediate refractive index layer 2c is set to 1.6.
The refractive index of the low refractive index layer 2b is set to 1.6 or more and 1.6 or less.
Smaller than

FIG. 4 also shows another antireflection film 10 of the present invention.
FIG. 4 is a layer configuration diagram of D. This anti-reflection film 10D also
Although the hard coat layer 4, the antireflection layer 2 and the antifouling layer 3 are formed on one surface of the film substrate 1, it is the same as the antireflection film 10A of FIG.
However, they differ in that they are composed of a single layer of the low refractive index layer 2b.

As described above, the antireflection layer 2 is formed of the low refractive index layer 2b.
When the optical film thickness nd is 1/4 of the wavelength λ of visible light, ie, nd = 1 / 4λ ₀ (where λ ₀ = center wavelength of antireflection). When the anti-reflection condition is satisfied, the reflectance becomes lowest at the wavelength of λ ₀ . Therefore, in order to satisfy this condition, in the antireflection film 10D, the low refractive index layer 2 is used.
The refractive index n _{L of} b is smaller than the refractive index of the film substrate 1, and preferably smaller than the refractive index of the hard coat layer 4.

As described above, in the present invention, as long as the antifouling layer 3 characteristic of the present invention is formed on the uppermost layer of the antireflection layer 2 of the antireflection film, the antireflection layer 2 itself is not used. Is not particularly limited.

FIG. 5 is a diagram showing a layer structure of the antireflection film 10E of the present invention, which is further different. This antireflection film 1
OE has a hard coat layer 4 on one side of a film substrate 1 and an antireflection layer 2 having a laminated structure of a total of four layers in which a high refractive index layer 2a and a low refractive index layer 2b are alternately laminated thereon. Is similar to the antireflection film 10A of FIG. 1 except that the antireflection film 3 does not have the antifouling layer 3 on the uppermost layer of the antireflection layer 2, The difference is that 2b ₃ itself has the function of the antifouling layer 3. That is, the uppermost low refractive index layer 2 b ₃ of the antireflection layer 2
It is made of a low refractive index material having water repellency and / or oil repellency, and its surface has a dynamic friction coefficient of 0.3 or less, more preferably 0.2 or less. Thus a low refractive index layer 2b ₃ is formed on the water-repellent and / or oil-repellent, and the dynamic friction coefficient of the surface 0.3 or less, more preferably to form the 0.2 or less, the formation material For example, a fluorine-containing organic compound such as perfluoroethylene can be used. Further, as a method of forming the kinetic friction coefficient of the surface to be 0.3 or less, preferably 0.2 or less, the above-mentioned fluorine-containing organic compound is inherently low in surface energy and easily obtains a surface having a low dynamic friction coefficient. Therefore, the surface may be formed so as to have a uniform and uniform surface.

FIG. 5 shows that the antireflection layer 2 has a high refractive index layer 2a.
And the low-refractive-index layer 2b are alternately laminated, and the low-refractive-index layer 2b as the uppermost layer has a function of an antifouling layer. However, the present invention is not limited to this. , Anti-reflection layer 2
The uppermost layer is made of a low-refractive index material having water repellency and / or oil repellency, and as long as its surface has a dynamic friction coefficient of 0.3 or less, a wide variety of layer configurations are included. For example, as shown in FIG.
In this case, the lower antireflection layer 2b of the antireflection layer 2 may be provided with the function of the antifouling layer without forming the antifouling layer 3, as shown in FIG. The antifouling layer 3 is also formed when the antireflection layer 2 has a layered structure in which an intermediate refractive index layer 2c, a high refractive index layer 2a, and a low refractive index layer 2b are sequentially laminated from the base film 1 side. Instead, the uppermost low refractive index layer 2b of the antireflection layer 2 may have the function of the above-described antifouling layer. Further, as shown in FIG. 4, the present invention can be applied to a case where the antireflection layer 2 is formed of a single layer of the low refractive index layer 2b.

The anti-reflection film of the present invention described above becomes an optical functional film having an anti-reflection function by being laminated with an optical functional film such as another plastic film or a deflecting film by lamination or the like.

The antireflection film or the optically functional film is bonded to a glass plate, a plastic plate, a deflection plate, etc. on the front surface of various display devices including a liquid crystal, a plasma display, and a CRT using an adhesive or an adhesive. This can provide the display with an antireflection function and an antifouling property. Therefore, it is possible to obtain a display device which is hardly damaged by the abrasion and which can easily recognize an image. Therefore, the present invention
Such an optical functional film, a display device provided with an antireflection film or an optical functional film on a display are also included.

[0048]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments.

Example 1 An antireflection film 10A having a layer structure shown in FIG. 1 was produced as follows. First, a transparent PET film (100 μm thick) was used as the film substrate 1, and a polyfunctional acrylic resin was formed thereon as a hard coat layer 4 by an ultraviolet irradiation curing method. On this, indium tin oxide (ITO) is used for the high refractive index layer 2a and silicon oxide is used for the low refractive index layer 2b, and the high refractive index layer 2a and the low refractive index layer 2b are alternately formed into a total of four layers. The laminated antireflection layer 2 was formed by a plasma-assisted vapor deposition method, and an antifouling layer 3 composed of perfluorosilane having a molecular number of 600 and fluorosilane having a molecular weight of 2,000 as a fluorine-containing organic compound was further applied and formed. The refractive index n, the shape thickness d, and the optical thickness nd of each layer were as shown in Table 1 below.

[0050]

[Table 1] Film substrate (PET film) n = 1.63 Hard coat layer n = 1.55, d = about 5 μm Anti-reflection layer: First layer (ITO) n _H = 2.05, nd = 60 nm Second layer (SiO _{2) n L = 1.46, nd} = 40nm 3 -layer _{(ITO) n H = 2.05,} nd = 110nm 4 -layer _{(SiO 2) n L = 1.46} , nd = 140nm antifouling layer (fluorine Containing organic compound) d = about 7 nm

In this case, the optical film thickness of each layer was monitored by an optical film thickness monitor, and when the target light amount was reached, the film formation was stopped to obtain a predetermined optical film thickness.

FIG. 6 shows the spectral reflection characteristics of the obtained antireflection layer 2 measured by absolute reflection.

The kinetic friction coefficient μ _K of the surface of the antifouling layer 3 of the antireflection film 10A was measured using a friction and wear analyzer shown in FIG.
Measured as S. Measurement Results of dynamic friction coefficient mu _K 0.1
It was one.

Further, steel wool (Bonstar No. 0)
000, manufactured by Nippon Steel Wool Co., Ltd.)
/ Cm ² was subjected to a scratch resistance test. As a result, it was found that scars were scarcely recognized and good scratch resistance was obtained.

Example 2 A transparent PET film (100 μm) was used as the film substrate 1.
m thickness), and a polyfunctional acrylic resin was formed thereon as a hard coat layer 4 by an ultraviolet irradiation curing method.
Then, an indium tin oxide (ITO) layer is formed as a high refractive index layer 2a, X having conductivity as a first layer on the hard coat layer 4 by a plasma assisted vapor deposition method, and a second layer is formed of silicon oxide. A low refractive index layer 2b is formed, and a high refractive index layer 2a made of zirconium oxide is formed as a third layer.
A low refractive index layer 2b made of silicon oxide was formed as a layer. Further, an antifouling layer 3 of perfluorosilane having a molecular weight of 600 and fluorosilane having a molecular weight of 5,000 was formed by coating as a fluorine-containing organic compound. Refractive index n of each layer, shape film thickness d,
The optical film thickness nd was as shown in Table 2 below.

[0056]

[Table 2] Film substrate (PET film) n = 1.63 Hard coat layer n = 1.55, d = about 5 μm Anti-reflection layer: First layer (ITO) n _H = 2.05, nd = 60 nm Second layer (SiO _{2) n L = 1.46, nd} = 40nm 3 -layer _{(ZrO 2) n H = 2.05} , nd = 110nm 4 -layer _{(SiO 2) n L = 1.46} , nd = 140nm antifouling layer ( Fluorine-containing organic compound) d = about 7 nm

In this case, the optical film thickness of each layer was monitored by an optical film thickness monitor, and when the target light amount was reached, the film formation was stopped to obtain a predetermined optical film thickness.

The spectral reflection characteristics of the obtained anti-reflection layer 2 by absolute reflection measurement were the same as those in Example 1 shown in FIG.

The dynamic friction coefficient μ _K of the surface of the antifouling layer 3 of the antireflection film was measured in the same manner as in Example 1.
The coefficient of kinetic friction μ _K was 0.08.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, it was found that scars were scarcely recognized and the sample had good scratch resistance.

Example 3 A transparent triacetyl cellulose film (TAC film) (80 μm thick) was used as the film substrate 1, and a polyfunctional acrylic resin was formed thereon as a hard coat layer 4 by an ultraviolet irradiation curing method. . Then, an indium tin oxide layer is formed as a high refractive index layer 2a on the first and third layers on the hard coat layer 4 by a sputtering method, and a low refractive index layer 2b is formed on the second and fourth layers. A silicon oxide layer was formed by a plasma assisted deposition method. Furthermore,
An antifouling layer 3 was formed by applying perfluorosilane having a molecular weight of 600 and fluorosilane having a molecular weight of 5000 as the fluorine-containing organic compound. Table 3 shows the refractive index n, the shape thickness d, and the optical thickness nd of each layer.

[0062]

[Table 3] Film base material (TAC film) n = 1.49 Hard coat layer n = 1.51, d = about 5 μm Anti-reflection layer: First layer (ITO) n _H = 2.05, nd = 58 nm Second layer (SiO _{2) n L = 1.46, nd} = 38nm 3 -layer _{(ITO) n H = 2.05,} nd = 125nm 4 -layer _{(SiO 2) n L = 1.46} , nd = 140nm antifouling layer (fluorine Containing organic compound) d = about 8 nm

In this case, the optical film thickness of each layer was monitored by an optical film thickness monitor, and when the target light amount was reached, the film formation was stopped to obtain a predetermined optical film thickness.

FIG. 8 shows the spectral reflection characteristics of the obtained antireflection layer 2 measured by absolute reflection.

The dynamic friction coefficient μ _K of the surface of the antifouling layer 3 of the antireflection film was measured in the same manner as in Example 1.
The coefficient of kinetic friction μ _K was 0.08.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, it was found that scars were scarcely recognized and the sample had good scratch resistance.

Example 4 An antireflection film 10C having the layer structure shown in FIG. 3 was produced as follows. First, a transparent TAC film (80 μm thick) was used as the film substrate 1, and a monofunctional acrylic resin was formed thereon as the hard coat layer 4 by an ultraviolet irradiation curing method. On the hard coat layer 4, an aluminum oxide layer is used as the first intermediate refractive index layer 2c, an indium tin oxide layer is used as the second high refractive index layer 2a, and an oxidized layer is used as the third low refractive index layer 2b. A silicon layer was formed by a plasma assisted deposition method. Further, as a fluorine-containing organic compound, perfluorosilane having a molecular weight of 600 and a molecular weight of 500
An antifouling layer 3 of fluorosilane No. 0 was applied and formed. The refractive index n, the shape thickness d, and the optical thickness nd of each layer were as shown in Table 4 below.

[0068]

[Table 4] Film substrate (TAC film) n = 1.49 Hard coat layer n = 1.51, d = about 5 μm Antireflection layer: First layer (Al ₂ O ₃ ) n _M = 1.65, nd = 110 nm 2 layers eyes _{(ITO) n H = 2.05,} nd = 125nm 3 -layer _{(SiO 2) n L = 1.46} , nd = 140nm antifouling layer (fluorine-containing organic compound) d = about 8nm

In this case, the optical film thickness of each layer was monitored by an optical film thickness monitor, and when the target light amount was reached, the film formation was stopped to obtain a predetermined optical film thickness.

FIG. 9 shows the spectral reflection characteristics of the obtained antireflection layer 2 measured by absolute reflection.

The dynamic friction coefficient μ _K of the surface of the antifouling layer 3 of the antireflection film was measured in the same manner as in Example 1.
The coefficient of kinetic friction μ _K was 0.08.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, it was found that scars were scarcely observed and the sample had good scratch resistance.

Example 5 An antireflection film 10D having a layer structure shown in FIG. 4 was produced as follows. First, a transparent PET film (100 μm thick) was used as the film substrate 1, and a monofunctional acrylic resin was formed thereon as a hard coat layer 4 by an ultraviolet irradiation curing method. Then, a silicon oxide layer was formed as a low refractive index layer 2b on the hard coat layer 4 by a plasma assisted vapor deposition method. Further, an antifouling layer 3 was formed by applying perfluorosilane having a molecular weight of 600 as a fluorine-containing organic compound. Refractive index n, shape thickness d, and optical thickness n of each layer
d is as shown in Table 5 below.

[0074]

[Table 5] Film substrate (PET film) n = 1.63 Hard coat layer n = 1.55, d = about 5 μm Antireflection layer: First layer (SiO ₂ ) n _L = 1.46, nd = 138 nm Antifouling layer ( Fluorine-containing organic compound) d = about 7 nm

In this case, the optical film thickness of each layer was monitored by an optical film thickness monitor, and when the target light amount was reached, the film formation was stopped to obtain a predetermined optical film thickness.

FIG. 10 shows the spectral reflection characteristics of the obtained antireflection layer 2 measured by absolute reflection.

The dynamic friction coefficient μ _K of the surface of the antifouling layer 3 of the antireflection film was measured in the same manner as in Example 1.
Dynamic friction coefficient mu _K was 0.15.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, it was found that scars were scarcely recognized and the sample had good scratch resistance.

Example 6 A transparent PET film (100 μm) was used as the film substrate 1.
m thickness), and a polyfunctional acrylic resin was formed thereon as a hard coat layer 4 by an ultraviolet irradiation curing method.
Then, a titanium oxide layer is formed as a high refractive index layer 2a on the first and third layers on the hard coat layer 4, and a silicon oxide layer is formed as a low refractive index layer 2b on the second and fourth layers by plasma-assisted deposition. It was formed by a method. Further, an antifouling layer 3 was formed by applying perfluorosilane having a molecular weight of 600 and fluorosilane having a molecular weight of 2,000 as a fluorine-containing organic compound. Refractive index n, shape thickness d, and optical thickness nd of each layer
Was as shown in Table 6 below.

[0080]

[Table 6] Film base material (PET film) n = 1.63 Hard coat layer n = 1.55, d = about 5 μm Antireflection layer: First layer (TiO ₂ ) n _H = 2.30, nd = 60 nm Second layer ( SiO ₂ ) n _L = 1.46, nd = 40 nm Third layer (TiO ₂ ) n _H = 2.30, nd = 110 nm Fourth layer (SiO ₂ ) n _L = 1.46, nd = 140 nm Antifouling layer (Fluorine-containing organic compound) d = about 7 nm

In this case, the optical film thickness of each layer was monitored by an optical film thickness monitor, and when the target light amount was reached, the film formation was stopped to obtain a predetermined optical film thickness.

FIG. 11 shows the spectral reflection characteristics of the obtained antireflection layer 2 by absolute reflection measurement.

The dynamic friction coefficient μ _K of the surface of the antifouling layer 3 of the antireflection film was measured in the same manner as in Example 1.
Dynamic friction coefficient mu _K was 0.12.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, it was found that scars were scarcely recognized and good scratch resistance was obtained.

Example 7 A transparent TAC film (80 μm
), And a polyfunctional acrylic resin was formed thereon as a hard coat layer 4 by an ultraviolet irradiation curing method. The first and third layers on the hard coat layer 4 are provided with a titanium oxide layer as a high refractive index layer 2a,
A silicon oxide layer was formed as a low refractive index layer 2b on the layer by a plasma assisted vapor deposition method. Further, perfluorosilane having a molecular weight of 600 as a fluorine-containing organic compound and a molecular weight of 5
An antifouling layer 3 of 000 fluorosilane was applied and formed. Refractive index n, shape thickness d, and optical thickness nd of each layer
Was as shown in Table 7 below.

[0086]

[Table 7] Film substrate (TAC film) n = 1.49 Hard coat layer n = 1.51, d = about 5 μm Anti-reflection layer: First layer (TiO ₂ ) n _H = 2.30, nd = 60 nm Second layer ( SiO ₂ ) n _L = 1.46, nd = 40 nm Third layer (TiO ₂ ) n _H = 2.30, nd = 110 nm Fourth layer (SiO ₂ ) n _L = 1.46, nd = 145 nm Antifouling layer (Fluorine-containing organic compound) d = about 7 nm

In this case, the optical film thickness of each layer was monitored by an optical film thickness monitor, and when the target light amount was reached, the film formation was stopped to obtain a predetermined optical film thickness.

FIG. 12 shows the spectral reflection characteristics of the obtained antireflection layer 2 measured by absolute reflection.

The dynamic friction coefficient μ _K of the surface of the antifouling layer 3 of the antireflection film was measured in the same manner as in Example 1.
The coefficient of kinetic friction μ _K was 0.08.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, it was found that scars were scarcely observed and good scratch resistance was obtained.

Example 8 An antireflection film was prepared by repeating Example 7 except that the thickness of the antifouling layer was about 8 nm.

The spectral reflection characteristics of the obtained anti-reflection layer 2 by absolute reflection measurement were the same as the characteristics of Example 7 shown in FIG.

The dynamic friction coefficient μ _K of the surface of the antifouling layer 3 of the antireflection film was measured in the same manner as in Example 1.
The coefficient of kinetic friction μ _K was 0.08.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, it was found that scars were scarcely recognized and the sample had good scratch resistance.

Example 9 An antireflection film 10E having the layer structure shown in FIG. 5 was produced as follows. First, a transparent TAC film (80 μm thick) was used as the film substrate 1, and a monofunctional acrylic resin was formed thereon as the hard coat layer 4 by an ultraviolet irradiation curing method. Then, a titanium oxide layer is formed as a high refractive index layer 2a on the first and third layers on the hard coat layer 4 and a silicon oxide layer is formed as a low refractive index layer 2b on the second layer by a plasma assisted vapor deposition method. It was further formed by sputtering tetrafluoroethylene resin as a low refractive index layer 2b ₃ having the antifouling function to the fourth layer of the uppermost layer.
The low refractive index layer 2b ₃ of the fourth layer to function as an antifouling layer, was not able to form this with separately antifouling layer. Refractive index n, shape thickness d, and optical thickness n of each layer
d is as shown in Table 8 below.

[0096]

[Table 8] Film substrate (TAC film) n = 1.49 Hard coat layer n = 1.50, d = about 5 μm Antireflection layer: First layer (TiO ₂ ) n _H = 2.30, nd = 75 nm Second layer ( SiO ₂ ) n _L = 1.46, nd = 38 nm Third layer (TiO ₂ ) n _H = 2.30, nd = 100 nm Fourth layer (tetrafluoroethylene resin) n _L = 1.38, nd = 145 nm

In this case, the optical film thickness of each layer was monitored by an optical film thickness monitor, and when the target light amount was reached, the film formation was stopped to obtain a predetermined optical film thickness.

The spectral reflection characteristics of the obtained antireflection layer 2 by absolute reflection measurement were the same as those shown in FIG.

The dynamic friction coefficient μ _K of the surface of the antifouling layer 3 of the antireflection film was measured in the same manner as in Example 1.
Dynamic friction coefficient mu _K was 0.15.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, it was found that scars were scarcely recognized and good scratch resistance was obtained.

Example 10 An antireflection film 10C having a layer structure shown in FIG. 3 was produced as follows. First, a transparent TAC film (80 μm thick) was used as the film substrate 1, and a monofunctional acrylic resin was formed thereon as the hard coat layer 4 by an ultraviolet irradiation curing method. An aluminum oxide layer as the first intermediate refractive index layer 2c on the hard coat layer 4, a zirconium oxide layer as the second high refractive index layer 2a, and a silicon oxide layer as the third low refractive index layer 2b. It was formed by a plasma assisted deposition method. Further, an antifouling layer 3 was formed by applying perfluorosilane having a molecular weight of 600 and fluorosilane having a molecular weight of 5,000 as fluorine-containing organic compounds. The refractive index n, the shape film thickness d, and the optical film thickness nd of each layer are shown in Table 9 below.
As shown.

[0102]

[Table 9] Film base material (TAC film) n = 1.49 Hard coat layer n = 1.51, d = about 5 μm Anti-reflection layer: First layer (Al ₂ O ₃ ) n _M = 1.65, nd = 125 nm 2 layers Eye (ZrO ₃ ) n _H = 2.05, nd = 255 nm Third layer (SiO ₂ ) n _L = 1.46, nd = 135 nm Antifouling layer (fluorine-containing organic compound) d = about 8 nm

In this case, the optical film thickness of each layer was monitored by an optical film thickness monitor, and when the target light amount was reached, the film formation was stopped to obtain a predetermined optical film thickness.

FIG. 13 shows the spectral reflection characteristics of the obtained antireflection layer 2 measured by absolute reflection.

The dynamic friction coefficient μ _K of the surface of the antifouling layer 3 of the antireflection film was measured in the same manner as in Example 1.
The coefficient of kinetic friction μ _K was 0.08.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, it was found that scars were scarcely observed and good scratch resistance was obtained.

Comparative Example 1 Example 2 was repeated except that the antifouling layer 3 was not formed, and an antireflection film of Comparative Example was produced.

The spectral reflection characteristics of the obtained anti-reflection layer 2 by absolute reflection measurement were the same as those in FIG.

The coefficient of kinetic friction μ _K of the surface of the antireflection film was measured in the same manner as in Example 1. As a result, the coefficient of kinetic friction μ _K was 0.42.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, it was found that there were several obvious scratches, fine scratches were observed, and that the scratch resistance was poor.

Comparative Example 2 Example 3 was repeated except that the antifouling layer 3 was not formed, and an antireflection film of a comparative example was produced.

The spectral reflection characteristics of the obtained antireflection layer 2 by absolute reflection measurement were the same as those in FIG.

The coefficient of kinetic friction μ _K of the surface of the antireflection film was measured in the same manner as in Example 1. The coefficient of kinetic friction μ _K was 0.44.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, it was found that there were several obvious scratches, fine scratches were observed, and the scratch resistance was poor.

Comparative Example 3 Example 5 was repeated except that the antifouling layer 3 was not formed, and an antireflection film of Comparative Example was produced.

The spectral reflection characteristics of the obtained anti-reflection layer 2 by absolute reflection measurement were the same as those in FIG.

The coefficient of kinetic friction μ _K of the surface of the antireflection film was measured in the same manner as in Example 1. As a result, the coefficient of kinetic friction μ _K was 0.40.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, several scratches were clearly found, and fine scratches were also observed, indicating that the scratch resistance was poor.

Comparative Example 4 Example 6 was repeated except that the antifouling layer 3 was not formed, and an antireflection film of Comparative Example was produced.

The spectral reflection characteristics of the obtained anti-reflection layer 2 by absolute reflection measurement were the same as those of FIG. 11 of Example 6.

The coefficient of kinetic friction μ _K on the surface of the antireflection film was measured in the same manner as in Example 1. As a result, the coefficient of kinetic friction μ _K was 0.37.

Further, a scratch resistance test was carried out in the same manner as in Example 1. As a result, several scratches were clearly found, and fine scratches were also observed, indicating that the scratch resistance was poor.

[0123]

The anti-reflection film of the present invention has an anti-reflection layer formed on at least one surface of a film substrate.
It has water repellency and / or oil repellency and has a dynamic friction coefficient on the surface of 0.3 or less, preferably 0.2 or less. Since the low refractive index layer having the water repellency and / or oil repellency and the dynamic friction coefficient is provided, the antifouling property and the scratch resistance of the antireflection film are improved. Therefore, the antireflection film of the present invention has very little reflection characteristic unevenness due to surface dirt and scratches on the surface due to abrasion, thereby preventing peeling of the antireflection layer.

In particular, in the antireflection film of the present invention, according to the aspect in which the conductive layer is provided on the antireflection layer, the antireflection film has an electromagnetic wave shielding function in addition to the above-described antifouling property and scratch resistance. Become. Further, according to the aspect in which the hard coat layer is formed between the base film and the antireflection layer, the mechanical strength is improved, and a more reliable antireflection film is obtained.

Further, when an optical functional film is produced by laminating the antireflection film of the present invention with another plastic film, a deflecting film or the like, the above-mentioned effects can be imparted to the obtained optical functional film.
In addition, by bonding these antireflection films and optical functional films to the front panel of the display of the display device, etc., the display is prevented from being scratched by abrasion, the display quality is improved, and the displayed image is more clearly displayed. Will be able to recognize. Further, the display device can maintain the initial appearance and the electromagnetic wave shielding effect over a long period of time.

[Brief description of the drawings]

FIG. 1 is a layer configuration diagram of an antireflection film of the present invention.

FIG. 2 is a layer configuration diagram of the antireflection film of the present invention.

FIG. 3 is a diagram showing the layer structure of the antireflection film of the present invention.

FIG. 4 is a layer configuration diagram of the antireflection film of the present invention.

FIG. 5 is a layer configuration diagram of the antireflection film of the present invention.

FIG. 6 is a spectral reflection characteristic diagram of an antireflection layer of an antireflection film of an example measured by absolute reflection.

FIG. 7 is an explanatory diagram of a friction and wear analysis device.

FIG. 8 is a spectral reflection characteristic diagram of the antireflection layer of the antireflection film according to the example measured by absolute reflection.

FIG. 9 is a spectral reflection characteristic diagram of the anti-reflection layer of the anti-reflection film of the example measured by absolute reflection.

FIG. 10 is a spectral reflection characteristic diagram of the anti-reflection layer of the anti-reflection film of the example measured by absolute reflection.

FIG. 11 is a spectral reflection characteristic diagram of an antireflection layer of an antireflection film of an example measured by absolute reflection.

FIG. 12 is a spectral reflection characteristic diagram of the anti-reflection layer of the anti-reflection film of the example measured by absolute reflection.

FIG. 13 is a spectral reflection characteristic diagram of the antireflection layer of the antireflection film according to the example measured by absolute reflection.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Film base material 2 Antireflection layer 2a High refractive index layer 2b Low refractive index layer 2b ₃ Low refractive index layer having an antifouling function 2c Intermediate refractive index layer 3 Antifouling layer 4 Hard coat layer X Conductive layer 10A, 10B, 10C, 10D, 10E Anti-reflection film

Continuation of the front page (72) Inventor Kazutoshi Kiyokawa 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd. (72) Inventor Haruo Uyama 1-15-1, Taito, Taito-ku, Tokyo Letterpress printing Inside (72) Inventor Hiroshi Kobayashi Inside Toppan Printing Co., Ltd., 1-1-1, Taito, Taito-ku, Tokyo

Claims (27)

[Claims] 1. An anti-reflection film having an anti-reflection layer on at least one surface of a film substrate, wherein an anti-fouling layer having water repellency and / or oil repellency is formed on the uppermost layer of the anti-reflection layer. An antireflection film, wherein the coefficient of dynamic friction of the surface of the antifouling layer is 0.3 or less. 2. The antireflection film according to claim 1, wherein the dynamic friction coefficient of the surface of the antifouling layer is 0.2 or less. 3. The antireflection film according to claim 1, wherein the antifouling layer comprises a fluorine-containing organic compound. 4. The anti-reflection layer comprises a high refractive index layer and a low refractive index layer alternately laminated on a film substrate.
3. The antireflection film according to any one of 3. 5. The antireflection film according to claim 4, wherein the total number of high refractive index layers and low refractive index layers alternately laminated on the film substrate is 2 to 6. 6. The antireflection film according to claim 1, wherein the antireflection layer comprises an intermediate refractive index layer, a high refractive index layer, and a low refractive index layer laminated on a film substrate. 7. The antireflection film according to claim 4, wherein the uppermost layer of the antireflection layer is a low refractive index layer. 8. An antireflection film having an antireflection layer on at least one surface of a film substrate, wherein the uppermost layer of the antireflection layer comprises a low refractive index layer having water repellency and / or oil repellency, The coefficient of dynamic friction of the surface of the refractive index layer is 0.
Antireflection film characterized by being 3 or less. 9. The anti-reflection film according to claim 8, wherein the coefficient of kinetic friction of the surface of the low refractive index layer as the uppermost layer of the anti-reflection layer is 0.2 or less. 10. The low refractive index layer as the uppermost layer of the antireflection layer,
The antireflection film according to claim 8, comprising a fluorine-containing organic compound. 11. An anti-reflection layer comprising a high refractive index layer and a low refractive index layer alternately laminated on a film substrate.
The antireflection film according to any one of claims 10 to 10. 12. The antireflection film according to claim 11, wherein the total number of high refractive index layers and low refractive index layers alternately laminated on the film substrate is 2 to 6. 13. The antireflection film according to claim 8, wherein the antireflection layer comprises an intermediate refractive index layer, a high refractive index layer, and a low refractive index layer laminated on a film substrate. 14. The antireflection film according to claim 1, wherein the antireflection layer includes a conductive layer. 15. The antireflection film according to claim 14, wherein the conductive layer contained in the antireflection layer is made of zinc oxide, indium oxide, tin oxide or a mixture of two or more thereof. 16. The antireflection film according to claim 14, wherein a metal dopant is mixed in the conductive layer included in the antireflection layer. 17. The antireflection film according to claim 16, wherein the metal dopant comprises aluminum, zinc, indium or tin. 18. The antireflection film according to claim 4, wherein the high refractive index layer of the antireflection layer has a refractive index of 1.8 or more. 19. The antireflection film according to claim 4, wherein the low refractive index layer of the antireflection layer has a refractive index of 1.6 or less. 20. The antireflection film according to claim 6, wherein the intermediate refractive index layer of the antireflection layer has a refractive index of 1.6 or more and 1.8 or less. 21. The antireflection film according to claim 1, wherein a hard coat layer is formed between the film substrate and the antireflection layer. 22. The antireflection film according to claim 21, wherein the hard coat layer is curable with ultraviolet light. 23. The antireflection film according to claim 21, wherein the hard coat layer is curable by an electron beam. 24. The antireflection film according to claim 21, wherein the hard coat layer is thermosetting. 25. A hard coat layer having an average particle size of 0.0
22. The antireflection film according to claim 21, comprising transparent fine particles of 1 to 3 µm. 26. An optical functional film having the antireflection film according to claim 1 on a surface. 27. A display device comprising a display having the antireflection film according to claim 1 on the surface.