JP2005017544A - Antireflection film and image display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a superior antireflection film which is used by being laminated or arranged on the surface of various flexible display apparatuses so as to softly follow the surface even though the film is strongly bent, and has superior adhesion and maintains optical functionality such as reflection prevention or the like and functions such as a gas shielding function or the like. <P>SOLUTION: The antireflection film has an antireflection layer consisting of a multilayer film having films of different refractive indexes and directly formed or through other layer on a flexible base material. The base material side layer among the antireflection layer is made of a silicon oxide which has an organic group including carbon atoms equal to greater than 10 atom% and equal to or less than 50 atom%. Moreover, at least one layer having inorganic oxide as a major component is formed on the layer of the base material side. The layer includes carbon atoms equal to or more than 1 atom% and equal to less than 10 atom% to provide a gas shielding function and flexibility. The image display device utilizes the film. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antireflection film and an image display device, and more specifically, various displays such as word processors, computers, and televisions, the surface of a polarizing plate used in a liquid crystal display device, a transparent plastic sunglasses lens, a prescription eyeglass lens, and a camera. It is used on the surface of optical lenses such as finder lenses, covers for various instruments, window glass for automobiles, trains, etc., and it can be flexibly tracked even when used for flexible displays. The present invention relates to an antireflection film excellent in gas barrier properties even under a high temperature and high humidity atmosphere, and an image display device using the same.
[0002]
[Prior art]
Conventionally, transparent substrates such as glass and plastic have been used for displays such as curved mirrors, rearview mirrors, goggles, window glass, televisions, personal computers and word processors, and various other commercial displays.
And in order to prevent light reflecting off the surface of a base material in order to read a character, a figure, and other information through a base material, those antireflection functions are given to those transparent base materials. .
In order to impart an antireflection function to a transparent substrate, for example, a multilayer film can be formed by laminating layers having different refractive indexes from an inorganic dielectric such as silicon oxide and titanium oxide on a transparent substrate. Are known.
For example, as an antireflection film to be attached to the outermost part of a display device, an antireflection film in which an antireflection film made of a three-layer laminated thin film made of an inorganic dielectric is formed on a substrate has been proposed (for example, Patent Literature 1).
[0003]
[Patent Document 1]
JP-A-8-129101
[0004]
As the layer structure of the antireflection film, the outermost layer (surface opposite to the base material layer) constituting the multilayer film has a small refractive index made of silicon oxide or the like in order to prevent light reflection. It is known to provide a layer, and as the inside of the outermost layer (interlayer between the base material layer and the outermost layer), one that forms one or more layers having a higher refractive index than the outermost layer is known. .
In addition, as a method for forming the antireflection film, it is known that a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method or an ion plating method, a chemical vapor deposition method such as a plasma CVD method, or the like is used. ing.
On the other hand, demand for thin, inexpensive and portable IT devices is increasing, and new displays such as a foldable flexible display have been proposed.
[0005]
[Problems to be solved by the invention]
However, when the inorganic dielectric is formed on a flexible substrate and used as an antireflection film, when the flexible substrate constituting the antireflection film is deformed, the inorganic dielectric is As a result, it is impossible to follow the flexible base material, and as a result, there is a disadvantage that the functions such as anti-reflection, adhesion, optical functionality, gas barrier, etc. are significantly reduced due to the occurrence of film cracking and film peeling. Furthermore, when such an antireflection film is used for a liquid crystal display, an organic electroluminescence display, or the like, there is a problem that a driving element and a light emitting element deteriorate.
In addition, if the antireflection film is used by being attached to the outermost part of the flexible display, the inorganic dielectric cannot follow the flexible display if the flexible base material constituting the flexible display is deformed. As a result, similar to the above, the occurrence of film cracking and film peeling has the drawback of significantly reducing functions such as adhesion, anti-reflection optical functionality, and gas barrier properties.
[0006]
[Means for Solving the Problems]
Therefore, in order to solve the above-mentioned problems, the present inventors have conducted intensive research, and as a result, the present invention has a different refractive index directly on the flexible substrate or through another layer. In the antireflection film for forming the antireflection layer comprising a multilayer film, the base layer side of the antireflection layer is composed of a silicon oxide layer containing 10 atomic% to 50 atomic% of carbon atoms, and It is characterized in that at least one layer containing an inorganic oxide as a main component and containing carbon atoms of 1 atomic% or more and 10 atomic% or less is formed on the substrate side layer, and has gas barrier properties and flexibility. When an antireflection film is manufactured, a liquid crystal display device, an organic electroluminescence (hereinafter also referred to as “EL”) display device, an inorganic EL display device, a plasma display (hereinafter referred to as “P”). In addition to the surface of various display devices such as “P”), it can be laminated or placed on the surface of various flexible display devices, and can flexibly follow even when strongly bent, It has excellent adhesion and can maintain functions such as optical functionality such as antireflection and gas barrier properties even in a high temperature and high humidity atmosphere.
Further, according to the present invention, in the above, the layer on the substrate side has a refractive index of 1.5 to 1.8 (wavelength λ = 550 nm), a film thickness of 5 nm to 300 nm. An antireflection film characterized by the above can be provided.
Of the layers formed on the substrate-side layer, the outermost layer has a refractive index of 1.4 to 1.5 (wavelength λ = 550 nm), a film thickness of 5 nm to 300 nm. It is possible to provide an antireflection film characterized by being a silicon oxide layer.
Further, in the layer formed on the substrate side layer, an intermediate layer is provided between the outermost layer and the substrate side layer, and the intermediate layer is a layer mainly composed of titanium oxide, Alternatively, it is a layer mainly composed of ITO (indium / tin oxide) and has a refractive index of 1.8 to 2.5 (wavelength λ = 550 nm), film thickness of 5 nm to 300 nm. There can be provided an antireflection film characterized in that there is.
In addition, it is possible to provide an optical functional film in which the antireflection layer is formed by vacuum deposition, ion plating, sputtering, or plasma CVD.
Moreover, in the above-mentioned antireflection film, a hard coat layer is provided, and an antireflection film can be provided.
In addition, an antireflection film characterized in that an antifouling layer is laminated on the uppermost layer can be provided.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The above-described present invention will be described in more detail below.
First, the antireflection film according to the present invention and the structure of a display device using the antireflection film will be described with reference to the drawings. FIG. 1 and FIG. 2 show the multilayer antireflection film according to the present invention. FIG. 3 is a schematic cross-sectional view showing a layer structure which is an embodiment of the antireflection film forming the film, and FIG. 3 is a schematic cross-sectional view showing an example of a liquid crystal display device having a display surface covered with the multilayer antireflection film according to the present invention. 4 and 5 are schematic views for explaining a method for producing an antireflection film for forming an optical functional film on the flexible substrate according to the present invention by plasma CVD.
[0008]
FIG. 1 is a schematic cross-sectional view showing a layer structure which is an embodiment of an antireflection film 36 for forming a multilayer antireflection film according to the present invention.
As shown in FIG. 1, the antireflection film 36 according to the present invention is formed by forming a plurality of antireflection layers on a flexible base material 30. The layer 13 is composed of a silicon oxide layer having an organic group containing carbon atoms, 10 atomic% or more and 50 atomic% or less, and the layer 14 formed on the layer on the substrate side is composed of carbon atoms, 1 atomic% or more and 10 atomic%. It is necessary to consist of an inorganic oxide layer containing:
This is because the anti-reflection film 36 according to the present invention has the above-described layer structure, whereby an optical functional film having both gas barrier properties and flexibility can be obtained.
[0009]
FIG. 2 is a schematic cross-sectional view showing a layer configuration of another aspect of the antireflection film 36 forming the multilayer antireflection film according to the present invention.
As shown in FIG. 2, the layer structure of the antireflection film according to the present invention comprises, from the outside, a low refractive index layer 15 / high refractive index layer 16 / medium refractive index layer 13 / flexible base material layer 30, It is an optical functional film having both gas barrier properties and flexibility.
In the antireflection layer, the outermost low refractive index layer 15 is composed of a silicon oxide layer composed of a layer containing 1 atomic% or more and 10 atomic% or less of carbon atoms.
The high refractive index layer 16 is made of a layer containing 1 atomic% or more and 10 atomic% or less of carbon atoms.
The medium refractive index layer 13 on the base material layer side is a silicon oxide layer that is composed of a layer containing 10 atomic% or more and 50 atomic% or less of carbon and has an organic group.
[0010]
Next, the antireflection film according to the present invention as described above, the material constituting the image display device, the production method thereof, etc. will be described. First, the antireflection layer constituting the antireflection film according to the present invention is a gas. It consists of multi-layered thin film layers with different refractive indices that have barrier properties and flexibility.
First, the antireflection layer 13 on the substrate side according to the present invention is not particularly limited as long as it is an inorganic-organic mixture containing carbon atoms of 10 atomic% to 50 atomic% and transparent in the visible region. It is preferable that the silicon oxide layer contains an organic substance in a range of a property ratio of 1.5 to 1.8 (wavelength λ = 550 nm), a film thickness of 5 nm to 300 nm.
As a raw material of silicon oxide containing organic substances, for example, organic silicone, silicon alkoxide, and the like are conceivable. These materials are widely used in the world, are safe, and vapor is formed when a film is formed by a vacuum film forming method. Since the pressure is high, there is an advantage that the raw material can be easily supplied.
Specific examples of raw materials for silicon oxide include silane, disilane, hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), methyltrimethoxysilane (MTMOS), methylsilane, dimethylsilane, trimethylsilane, and diethylsilane. , Si compounds such as propylsilane, phenylsilane, tetramethoxysilane, octamethylcyclotetrasiloxane, tetraethoxysilane, and hexamethylsilazane.
The reason why it is necessary to contain 10 atomic% or more and 50 atomic% or less of carbon atoms as a material constituting the layer 13 on the substrate side according to the present invention is that the antireflection layer on the substrate side is in the above range. By forming a silicon oxide layer containing carbon atoms and having an organic group, an antireflection layer (upper layer) 13 mainly composed of an inorganic material and a flexible base material (lower layer) 30 mainly composed of an organic material. With excellent adhesion to the film, it does not cause film cracking or peeling, can maintain optical properties (antireflection function), can flexibly follow the handling of the antireflection film, and the silicon oxide layer Can be set to a desired refractive index, which is preferable.
Moreover, even if it deform | transforms by laminating | stacking or arrange | positioning and using the antireflection film which concerns on said this invention on the surface of various flexible display apparatuses, while maintaining an antireflection function, it can follow flexibly. There is an advantage that can be.
On the other hand, in the base-side antireflection layer 13 according to the present invention, if the carbon atom content is less than 10 at%, the flexibility is inferior, and the underlying flexible base material cannot be followed. It is not preferable because it causes film cracking and peeling and causes a decrease in the antireflection function.
On the other hand, when the content of carbon atoms exceeds 50 Atomic%, the silicon oxide film is colored yellow or the transparency of the silicon oxide film is lowered, which is suitable as an antireflection functional multilayer film of the antireflection film. It cannot be used, and the gas barrier property is also deteriorated.
[0011]
In the antireflection layer according to the present invention, the optical characteristics (antireflection function) required for the layer 13 on the substrate side are a refractive index of 1.5 or more and 1.8 or less (wavelength λ = 550 nm). It is necessary to be in the range.
[0012]
In addition, the thickness of the antireflection layer 13 on the substrate side in the present invention is not particularly limited and may be any thickness as long as it can exhibit flexibility and an antireflection effect, but about 5 nm to 300 nm. Particularly preferred is about 50 nm to 150 nm.
If the thickness of the layer is less than 5 nm, the flexibility and the antireflection effect are lowered, which is not preferable. On the other hand, if the thickness of the layer is more than 300 nm, the adhesion and the like are lowered, which is not preferable.
[0013]
Next, in the antireflective layer according to the present invention, the low refractive index layer further formed on the antireflective layer on the substrate side contains a carbon atom content in the range of 1 atomic% to 10 atomic%. It is necessary to consist of an inorganic oxide layer.
This is because a dense film is formed by forming an inorganic oxide layer containing carbon atoms in the above-mentioned range on the layer on the substrate side, so that optical functionality (antireflection function) with excellent gas barrier properties is achieved. It has the advantage of forming a layer.
In addition, since it is an antireflection layer that is further formed on a middle refractive index layer (base layer side) that is excellent in flexibility, it is laminated or disposed on the surface of an antireflection film or various flexible display devices. In the case of being used, there is an advantage that even if it is deformed, it can flexibly follow, and the gas barrier property and antireflection function can be maintained.
On the other hand, if the carbon atom content exceeds 10 Atomic%, there is a problem in that the barrier property of water vapor or gas is deteriorated, or a problem that the desired refractive index cannot be set.
[0014]
In addition, the thickness of the antireflection layer 14 further formed on the antireflection layer on the substrate side in the present invention is not particularly limited, and any thickness can be used as long as flexibility and an antireflection effect can be obtained. However, about 5 nm to 300 nm is particularly preferable, and about 50 nm to 150 nm is more preferable.
If the thickness of the layer is less than 5 nm, it is not preferable because gas barrier properties and antireflection effects are not achieved. On the other hand, if the thickness of the layer is more than 300 nm, adhesion and antireflection ability are deteriorated, which is not preferable.
[0015]
When a plurality of layers are formed on the substrate side layer, the outermost layer 15 has a refractive index of 1.4 or more and 1.5 or less (wavelength λ = 550 nm), a film thickness of 5 nm or more. A silicon oxide layer containing 300 nm or less and 1 atom% or more and 10 atom% or less of carbon atoms is preferable.
This is because when the silicon oxide has a low refractive index, the anti-reflection effect is great when the optical functional film is formed in multiple layers.
Further, the uppermost layer 15 preferably has a carbon atom ratio of 10 atomic% or less, and more preferably does not contain an organic component.
This has an advantage of forming an optical functional (antireflection function) layer having excellent gas barrier properties because it becomes a dense film by not containing an organic component.
As the material constituting the outermost layer 15, in addition to the silicon oxide material, a raw material containing fluorine can also be suitably used.
This has the advantage that a low refractive index and water repellency can be improved by containing a fluorine-based material.
On the other hand, if the proportion of carbon atoms is more than 10 atomic%, the gas barrier property is deteriorated and the refractive index is increased, so that the desired antireflection function is lowered.
Further, the silicon oxide film of the outermost layer 15 is mainly intended to be used as a single layer in the antireflection multilayer film constituting the antireflection film 36, more specifically as a low refractive index layer. Is preferably in the above range.
Regarding the thickness of the silica layer, the antireflection film of the present invention is not particularly limited and is not particularly limited as long as it has a thickness that exhibits an antireflection effect, but is preferably 5 nm to 300 nm, preferably 50 nm. A range of ˜150 nm is more preferable.
When the layer thickness is less than 5 nm, even if a film is formed on the flexible substrate, it is not preferable because the antireflection effect may not be achieved. When it exceeds 300 nm, adhesion and antireflection function are not possible. Is unfavorable because it decreases.
[0016]
A plurality of layers formed on the substrate side layer are formed, and a layer (intermediate layer) 16 provided inside the outermost layer has a refractive index of 1.8 to 2.5 (wavelength λ = 550 nm), the film thickness is in the range of 5 nm to 300 nm, and it is preferably composed of a layer containing 1 atomic% or more and 10 atomic% or less of carbon atoms.
Specific examples of the material constituting the intermediate layer 16 of the antireflection layer according to the present invention include titanium oxide, ITO (indium / tin oxide), silicon nitride, silicon oxynitride, tantalum oxide, and zinc oxide. Tin oxide, niobium oxide, hafnium oxide, and the like can be used.
Furthermore, by using a metal material, gas barrier properties and antireflection performance can be improved. For example, metals such as copper, chromium, nickel, molybdenum, titanium nitride, silver, gold, titanium, and aluminum are used. be able to.
Among them, a material mainly composed of titanium oxide or ITO is preferable because it is a high refractive index material having a refractive index of 1.8 or more and has a high gas barrier property.
Examples of the organic metal raw material for titanium oxide include titanium tetraisopropoxide (TTIP), titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetra n-butoxide, and titanium tetra t-butoxide. , Titanium tetra sec-butoxide, titanium tetrachloride, and the like can be used. Among them, titanium tetraisopropoxide (TTIP) and titanium tetra t-butoxide can be used.
In addition, since the ITO film often causes a decrease in conductivity and transmittance when irregular materials are mixed, the organic content is preferably 10 atomic% or less.
[0017]
The optical characteristics (antireflection function) required for the intermediate layer 16 according to the present invention are a refractive index of 1.8 or more and 2.5 or less (wavelength λ = 550 nm).
Since the intermediate layer 16 of the present invention is mainly intended to be used as a single layer in the antireflection multilayer film constituting the antireflection film, more specifically as a high refractive index layer, its refractive index is in the above range. It is preferable that
This is not preferable if the refractive index is less than 1.8 because it cannot be suitably used as a high refractive index layer.
By using the high refractive index layer as described above, the antireflection function is enhanced with a synergistic effect with other thin layers (for example, the low refractive index layer such as the silicon oxide film) in the antireflection multilayer film. Can do.
Regarding the thickness of the high refractive index layer, the antireflection film of the present invention is not particularly limited as long as it has a thickness that exhibits an antireflection effect without any particular limitation, but is preferably 5 nm to 300 nm. A range of 5 nm to 150 nm is more preferable.
When the layer thickness is less than 5 nm, even if a film is formed on the flexible substrate, the antireflection effect may not be achieved, and this is not preferable. When it exceeds 300 nm, the visible light transmittance decreases. This is not preferable.
[0018]
Here, the position where the high refractive index layer is provided is not particularly limited, and the present invention can be provided at any position as long as the antireflection function improves as a whole. As shown in FIG. 2, the high refractive index layer and the low refractive index layer can efficiently prevent reflection of light when they are in contact with each other. Therefore, the high refractive index layer is composed of the low refractive index layer and the middle refractive index layer. It is preferable to install between them.
[0019]
Next, as the base material 30 of the antireflection film according to the present invention, it is a portion that becomes the foundation of the antireflection film.
The flexible substrate is not particularly limited as long as it is a polymer film transparent in the visible light range. Specifically, for example, a triacetyl cellulose film, a diacetyl cellulose film, an acetate butyrate cellulose film, a polyether Sulphone film, polystyrene resin film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate resin film, polysulfone film, cyclic olefin resin film, polyether film, trimethylpentene film, polyether ketone film , Polyethersulfone film, acrylonitrile film, acrylonitrile-styrene copolymer resin (AS resin) film, acrylonitrile-butadiene-styrene copolymer Fat (ABS resin) film, polyamide resin film, fluororesin film, acetal resin film, a cellulose-based resin film or the like can be used.
Among these, a colorless and transparent stretched film is preferable, and a uniaxial or biaxially stretched polyester film is more preferable because it is excellent in transparency and heat resistance.
Further, triacetyl cellulose is also preferable from the viewpoint of no optical anisotropy.
The thickness of the flexible substrate is usually preferably about 6 μm to 500 μm.
The flexible substrate of the present invention may be colored as long as it is essentially transparent, and may be provided with a pattern, characters, or the like by printing or the like.
[0020]
Moreover, as the antireflection film 36 shown in FIGS. 1 and 2, a hard coat layer 31 can also be provided.
The hard coat layer 31 used in the present invention is a layer formed for the purpose of imparting strength to the antireflection film of the present invention. Therefore, it is not an essential layer depending on the use of the antireflection film.
[0021]
The material for forming the hard coat layer 31 is not particularly limited as long as it is a transparent material in the visible light region and can give strength to the antireflection film. It is preferable to show a hardness of “H” or higher in a pencil hardness test shown in JIS K5600-5-4.
Specifically, it is preferable to use a thermosetting resin and / or an ionizing radiation curable resin, and more specifically, those having an acrylate functional group, for example, a relatively low molecular weight polyester, Ether, acrylic resin, epoxy resin, polyurethane, alkyd resin, spiroacetal resin, polybutadiene, polythiol polyene resin, polyfunctional compound (meth) acrylate (hereinafter referred to as acrylate and methacrylate (meth) Monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, vinyltoluene, N-vinylpyrrolidone and the like, which are reactive diluents and oligomers or prepolymers such as acrylate) Monomers, such as trimethylol Lopantri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6 -What contains hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. is used suitably.
As the film thickness of the hard coat layer, those in the range of usually 1 to 30 μm are preferably used.
The formation method can use a normal coating method, and is not particularly limited.
[0022]
Although the hard coat layer 31 is provided, the purpose of providing the hard coat is to give the antireflection film strength and not to improve the antireflection function. It is preferable to install it at a position away from the base material.
[0023]
As the antireflection film of the present invention, an antifouling layer 35 may be provided on the uppermost silica layer.
The antifouling layer is formed in order to prevent dust or dirt from adhering to the antireflection film disposed on the front surface of the display panel, or to facilitate removal even if adhering. Specifically, a surfactant such as a fluorosurfactant, a paint containing a fluororesin, a release agent such as silicone oil, or a wax is applied in a very thin range as long as the optical function such as antireflection is not deteriorated. Wipe away any excess. Although the antifouling layer may be formed as a permanent layer, it may be formed by coating whenever necessary. The thickness of the antifouling layer 35 is preferably 1 to 30 nm.
If it exceeds 30 nm, an optical effect is produced, and the optical properties as an antireflection film are deteriorated.
[0024]
As the antireflection film of the present invention, an adhesive layer may be provided on the surface of the flexible substrate on which the inorganic oxide thin film is not formed.
Any adhesive or adhesive may be used for the adhesive layer, but it is preferable to use an adhesive resin having a low glass transition temperature or a mixture of a rubber elastic thermoplastic elastomer and a wax. it can.
Specifically, for example, acrylic resins and silicone resins are used as adhesive resins having a low glass transition temperature, and examples of thermoplastic elastomers having rubber elasticity include ethylene-vinyl acetate copolymers and butadiene rubbers. Synthetic rubber such as styrene-butadiene rubber, nitrile rubber, nitrile-butadiene rubber, high styrene rubber, acrylic rubber, natural rubber, and the like can be used.
The adhesive layer is formed by a roll coater, a die coater, a blade coater or the like.
[0025]
Examples of the method for forming the high refractive index layer and the low refractive index layer constituting the antireflection layer according to the present invention on a flexible substrate include, for example, the above-described materials by plasma chemical vapor deposition (CVD), It can be formed or laminated by a thin film forming method such as a thermal CVD method, a vacuum deposition method, a sputtering method, a wet coating method such as a sol-gel method, or an ion plating method.
Among these, by using the plasma CVD method, conditions such as film density, film thickness, and refractive index when forming the silica layer can be controlled relatively easily, so that gas permeability and adhesion to a glass substrate can be achieved. This is preferable because it has an advantage that an optical functional film having both of these properties in a balanced manner can be formed.
In addition, when the silicon oxide film of the present invention is composed of a silicon compound containing an organic group, a thin film with a stable plasma CVD method and sputtering method using a raw material in a gaseous state can be formed. Since a plurality of thin layers can be formed at the same time, the productivity can be improved, which is preferable.
[0026]
FIG. 4 is a schematic view for explaining a method for producing an antireflection film according to the present invention by plasma CVD.
As shown in FIG. 4, as a method for producing a film in which an antireflection layer is formed on a flexible substrate using a plasma CVD apparatus, first, a web-like polymer film (flexible substrate) 1 is used. It is unwound from the substrate unwinding section 2 and introduced into the plasma CVD reaction chamber 4 in the vacuum vessel 3.
The entire reaction vessel 3 is evacuated by a vacuum pump 5. At the same time, a raw material gas having a specified flow rate is supplied to the reaction chamber 4 from the raw material gas inlet 6, and the interior of the reaction chamber 4 is always filled with these gases at a constant pressure.
[0027]
Next, the polymer film 1 unwound from the substrate unwinding section 2 and introduced into the reaction chamber 4 is wound around the film-forming drum 8 through the reverse roll 7 and is synchronized with the rotation of the film-forming drum 8. While being sent in the direction of the reverse roll 7 '.
Next, an RF voltage is applied between the electrode 9 and the film forming drum 8 by the power supply 10.
At this time, the frequency of the power source is not limited to a radio wave, and an appropriate frequency from a direct current to a microwave can be used.
Then, by applying an RF voltage between the electrode 9 and the film forming drum 8, plasma 11 is generated around these electrodes.
Then, the raw material gas reacts in the plasma 11 to generate an inorganic oxide, which is deposited on the polymer film 1 wound around the film-forming drum 8 to form an antireflection film 12.
Thereafter, the polymer film 1 having the antireflection film 12 formed on the surface thereof is wound up by the substrate winding portion 2 ′ through the reverse roll 7 ′.
In the present invention, the refractive index, film thickness, composition, density, and the like of the formed antireflection film 12 can be controlled over a wide range by controlling the temperature, material gas flow rate / pressure, discharge conditions, and feed rate of the polymer film 1. Therefore, the antireflection film 12 having desired gas permeability, flexibility, and optical characteristics can be obtained without changing the material.
[0028]
FIG. 5 is a schematic view of another embodiment for explaining the production method of the antireflection film according to the present invention by the plasma CVD method.
For production of the antireflection film, a plasma CVD apparatus as shown in FIG. 5 can also be used.
The plasma CVD apparatus is a capacitively coupled plasma CVD apparatus, and its basic structure and principle are the same as the apparatus of FIG.
Therefore, also in the apparatus, the web-like polymer film 21 is unwound from the substrate unwinding portion 22 and introduced into the reaction chambers (a, b, c) in the vacuum vessel 23. Then, a predetermined film is formed on the film-forming drum 24 in the reaction chamber, and is taken up by the substrate take-up unit 26.
[0029]
Therefore, also in the apparatus, the web-like polymer film 21 is unwound from the substrate unwinding portion 22 and introduced into the reaction chambers (a, b, c) in the vacuum vessel 23. Then, a predetermined film is formed on the film-forming drum 24 in the reaction chamber, and is taken up by the substrate take-up unit 26.
[0030]
The difference between the apparatus shown in FIG. 5 and the apparatus shown in FIG. 4 is that the apparatus shown in FIG. 4 has only one reaction chamber for forming an antireflection film on the film. The plasma CVD apparatus shown has a plurality of (three) reaction chambers. Each reaction chamber (a, b, c) is formed by being isolated by an isolation wall 25. Here, for convenience of the following description, the three reaction chambers are referred to as a reaction chamber a, a reaction chamber b, and a reaction chamber c from the right side. In each reaction chamber, electrode plates a1, b1, c1 and source gas inlets a2, b2, c2 are installed, respectively.
[0031]
Each reaction chamber (a, b, c) is installed along the outer periphery of the film-forming drum 24. This is because the plastic film on which the laminated film is formed is inserted into the reaction chamber in synchronism with the film-forming drum 24 as described in the example shown in FIG. 5, and a multilayer film is formed on the film-forming drum. This is because each film can be laminated continuously by arranging in this manner.
In the apparatus shown in FIG. 5, the number of reaction chambers is three. However, the plasma CVD apparatus used in the method for producing an antireflection film of the present invention is not limited to this, and may be changed as necessary. be able to.
[0032]
According to the plasma CVD apparatus as described above, it is possible to form a film independently in each reaction chamber by changing the source gas introduced into each reaction chamber. When a multilayer film of silica and a silica film is formed on a plastic film, a gas containing an organic titanium compound is introduced into the reaction chamber b, and a gas containing silicon is introduced into the reaction chamber a and the reaction chamber c. An antireflection film in which a titanium oxide film and a silica film are formed on the plastic film 21 can be formed before the plastic film 21 is wound on the substrate winding portion 26 through the film forming drum 25.
[0033]
Furthermore, in the above case, the gas introduced into the reaction chamber a and the reaction chamber c is a gas containing silicon, but the conditions in each reaction chamber, for example, the flow rate and pressure of the gas, the discharge conditions, etc. are changed. Thus, it is possible to change the characteristics of the silica film formed between the reaction chamber a and the reaction chamber c. With this apparatus, it is possible to freely combine titanium oxide films, silica films, and the thickness, composition, density, refractive index, and the like of these films.
[0034]
Further, it is not always necessary to introduce different source gases into the respective reaction chambers. For example, a titanium oxide film is formed by introducing a gas containing an organic titanium compound into all of the reaction chambers a, b, and c shown in FIG. Thereafter, all the gases once introduced into the reaction chambers a, b, and c are removed, and a gas containing silicon is newly introduced into the reaction chambers a, b, and c to form a silica film on the titanium oxide film. Is possible.
[0035]
In the present invention, a laminated film in which a titanium oxide film and a silica film are formed on a plastic film may be formed by processing the plastic film a plurality of times with the apparatus shown in FIG. 4 described above. However, as described above, the antireflection film in which the titanium oxide film and the silica film are formed on the plastic film is formed by processing the plastic film at a time using the apparatus shown in FIG. Good. Moreover, it is also possible to obtain an antireflection film in which a plurality of titanium oxide films and silica films are alternately laminated by processing a plastic film a plurality of times using the apparatus shown in FIG. Further, an ITO film using a sputtering method can be manufactured by the same method.
[0036]
FIG. 3 is a schematic sectional view showing an example of an image display device in which the display surface of the glass substrate is coated with the antireflection film according to the present invention.
As the image display device according to the present invention, as shown in FIG. 3, a polarizing plate having a layer structure composed of an antireflection film layer 36 / a polarizing element 38 / TAC film layer 37 is laminated on a liquid crystal display element, Further, a polarizing plate having a layer structure composed of TAC film 37 / polarizing element 38 / TAC film 37 is laminated on the other surface of the liquid crystal display element.
[0037]
Specifically, the antireflection film layer of FIGS. 1 and 2 obtained above is the outermost layer (the layer on the opposite side of the layer in contact with the base material), and from the antireflection film layer toward the base material. An antireflection film layer, for example, an antireflection film layer 36 having a layer structure comprising an antifouling layer 35 / a silicon oxide film 32 / a titanium oxide film 33 / a silicon oxide film 34 / a hard coat layer 31 / a base material layer 30; The element 38 and a TAC film 37 as a base material layer are laminated, and the layer configuration is an antireflection film layer 36 / polarizing element 38 / TAC film layer 37.
In addition, the adhesive may be apply | coated to the lower surface of the antireflection film of this invention, In this case, an antireflection film can be stuck and used for the object which should be antireflective, for example, glass etc. . Further, the backlight is irradiated from the lower side of FIG.
The antireflection film of the present invention is usually disposed on the light exit side of the backlight, but the antireflection film of the present invention may be further used in place of the TAC film on the bottom surface.
In the STN liquid crystal display device, a retardation plate is inserted between the liquid crystal display element and the polarizing plate. In addition, an adhesive layer is provided between the layers of the liquid crystal display device as necessary.
[0038]
As the polarizing element 38 constituting the image display device according to the present invention, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer system saponified by dyeing and stretching with iodine or a dye. A film or the like can be used.
In order to increase adhesiveness and prevent static electricity in the laminating process, when the transparent base film of the antireflection film is a TAC film, for example, the TAC film is subjected to a saponification process. This saponification treatment may be performed either before or after the hard coat layer is applied to the TAC film.
[0039]
Thus, in addition to the above liquid crystal display device using the antireflection film or polarizing element according to the present invention, although not shown, an organic EL (electroluminescence) display device, an inorganic EL display device, a plasma display, a flexible display It can be used as a material for various display surfaces, etc., and by laminating or arranging the optical functional film according to the present invention on the observation side of the image display unit, film peeling does not occur, transparency, Optical properties, adhesion, and strength can be maintained, and performance that is excellent in appearance, gas permeability, and productivity is exhibited.
[0040]
【Example】
Next, the present invention will be specifically described with reference to examples.
(Example 1)
A triacetyl cellulose film (product name: Fujitac, manufactured by Fuji Photo Film Co., Ltd., refractive index) subjected to saponification treatment of 80 μm as a flexible substrate (polymer film) by plasma CVD using the apparatus of FIG. 1.50) A hard coat layer having a thickness of 6 μm was formed thereon. The refractive index of this hard coat layer was 1.51.
Further, a silicon oxide film (first layer) is formed in the reaction chamber a shown in FIG. 5, a titanium oxide film (second layer) is formed in the reaction chamber b, and a silicon oxide film (third layer) is formed in the reaction chamber b by the plasma CVD method. I tried to do it.
A 13.56 MHz RF power source was used as the high frequency power source, and the feeding speed of the polymer film as the base material during continuous film formation was adjusted according to the film thickness of each layer. Other conditions are as follows.
<First Layer: Silicon Oxide Film Formation Conditions (Reaction Chamber a)>
Applied power 1kW
Oxygen gas flow rate 100sccm
Hexamethyldisiloxane gas flow rate 1000sccm
Deposition pressure 4Pa
<Second Layer: Titanium Oxide Film Formation Conditions (Reaction Chamber b)>
Applied power 1kW
Oxygen gas flow rate 3000sccm
Titanium tetraisopropoxide gas flow rate 100sccm
Deposition pressure 6Pa
<Third layer: Conditions for forming silicon oxide film (reaction chamber c)>
Applied power 1kW
Oxygen gas flow rate 3000sccm
Tetramethoxysilane gas flow rate 800sccm
Deposition pressure 9Pa
[0044]
The gas flow unit sccm is a standard cubic cm per minute.
[0045]
The measurement results of the antireflection film (optical functional film) formed on the TAC film under the above conditions are shown below.
<First layer: measurement result of silicon oxide film>
Film thickness 118nm
Film composition (Atomic%) Si: C: O = 35: 35: 30
Refractive index (λ = 550 nm) 1.70
<Second layer: measurement result of titanium oxide film>
Film thickness 20nm
Film composition (Atomic%) Ti: C: O = 35: 5: 60
Refractive index (λ = 550 nm) 2.20
<Third layer: measurement result of silicon oxide film>
Film thickness 120nm
Film composition (Atomic%) Si: C: O = 35: 1: 64
Refractive index (λ = 550 nm) 1.45
<Measurement result of antireflection film>
Layer structure: silicon oxide film / titanium oxide film / silicon oxide film
Oxygen permeability 0.1 cc / m ² / Day (23 ° C., 0% Rh)
Water vapor transmission rate 0.1g / m ² / Day (38 ° C, 100% Rh)
Visibility reflectance 0.42%
<Apparatus used for measurement of antireflection film>
Composition analysis Photoelectron spectrometer
Model number ESCALAB220i-XL Manufacturer VG Scient
Refractive index / Visibility reflectance / Film thickness Spectrophotometer
Model number UV-3100PC Manufacturer Shimadzu
Oxygen permeability Oxygen gas permeability measuring device
Model Number OX-TRAN 2/20 Manufacturer MOCON
Water vapor transmission rate Water vapor transmission rate measuring device
Model number PERMATRAN-W 3/31 Manufacturer MOCON
[0051]
As shown in the results of the formation of the antireflection film described above, the optical reflectivity reflectance is 0.42%, the carbon atom content of the silicon oxide film (first layer), 30 at%, and the titanium oxide film. (Second layer) and carbon atom content of silicon oxide film (third layer), 10 at% or less, oxygen permeability, 2 cc / m ² / Day, water vapor transmission rate, 0.1 g / m ² / Day antireflection film is formed on TAC film, layer structure, silicon oxide film (third layer) / titanium oxide film (second layer) / silicon oxide film (first layer) / hard coat layer / TAC film An antireflection film according to the present invention was obtained.
The antireflection film according to the present invention obtained above is laminated not only on the surface of various display devices such as liquid crystal display devices, organic EL display devices, inorganic EL display devices, and PDPs, but also on the surfaces of flexible various display devices, Or it can be placed and used, and it can follow flexibly even if it is bent strongly, and it has excellent adhesion, and furthermore, even in a high temperature and high humidity atmosphere, it has optical functions such as anti-reflection and gas barrier properties. It was possible to maintain functions such as
(Experimental example)
Based on JIS K 5600-5-1, the antireflection film formed above is sandwiched between test plates so that the antireflection film surface is bent outward, and is bent at an angle of 180 degrees uniformly at the same speed over 2 seconds. After the bending test of the cylindrical mandrel method (mandrel diameter, 8 mm, bending time, 2 seconds), no film cracking or peeling was observed in the antireflection film, and the film was bent with a uniform and good film quality. In the oxygen permeability after the test and the water vapor permeability, the oxygen permeability is 0.1 cc / m. ² / Day, water vapor transmission rate, 0.2 g / m ² / Day, gas barrier properties were maintained, film cracking or peeling from the substrate was not observed, and the film was excellent in flexibility.
Example 2
A triacetyl cellulose film (product name: Fujitac, manufactured by Fuji Photo Film Co., Ltd., refractive index) subjected to saponification treatment of 80 μm as a flexible substrate (polymer film) by plasma CVD using the apparatus of FIG. 1.50) A hard coat layer having a thickness of 6 μm was formed thereon. The refractive index of this hard coat layer was 1.51.
Further, a silicon oxide film (first layer) is formed by a plasma CVD method in the reaction chamber a shown in FIG. ₂ O ₃ An ITO film (second layer) containing as a main component was formed by a sputtering method, and in c, a silicon oxide film (third layer) was formed by a plasma CVD method.
A 13.56 MHz RF power source was used as the high frequency power source, and the feeding speed of the polymer film as the base material during continuous film formation was adjusted according to the film thickness of each layer. Other conditions are as follows.
<First Layer: Silicon Oxide Film Formation Conditions (Reaction Chamber a)>
Applied power 1kW
Oxygen gas flow rate 100sccm
Hexamethyldisiloxane gas flow rate 1000sccm
Deposition pressure 4Pa
<Second layer: ITO film formation conditions (reaction chamber b)>
Applied power 5kW
Introduction gas flow rate Argon, oxygen
Deposition pressure 0.3Pa
<Third Layer: Film Formation Conditions for Silicon Oxide Film (Reaction Chamber c)>
Applied power 1kW
Oxygen gas flow rate 3000sccm
Tetramethoxysilane gas flow rate 800sccm
Deposition pressure 9Pa
[0057]
The measurement results of the antireflection film (optical functional film) formed on the TAC film under the above conditions are shown below.
The apparatus used for the measurement of the antireflection film of Example 2 was the same as that of Example 1.
<First layer: measurement result of silicon oxide film>
Film thickness 96nm
Film composition (Atomic%) Si: C: O = 34: 35: 31
Refractive index (λ = 550 nm) 1.70
<Second layer: measurement result of ITO film>
Film thickness 41nm
Refractive index (λ = 550 nm) 1.98
<Third layer: measurement result of silicon oxide film>
Film thickness 103nm
Film composition (Atomic%) Si: C: O = 35: 1: 64
Refractive index (λ = 550 nm) 1.45
<Measurement result of antireflection film>
Layer structure: silicon oxide film / ITO film / silicon oxide film
Oxygen permeability 0.1 cc / m ² / Day (23 ° C., 0% Rh)
Water vapor transmission rate 0.1g / m ² / Day (38 ° C, 100% Rh)
Visibility reflectance 0.35%
[0062]
As shown in the results of the formation of the antireflection film described above, it has a luminous reflectance, an optical characteristic of 0.35%, a carbon atom content of the silicon oxide film (first layer), 35 at%, an ITO film ( Second layer) and silicon oxide film (third layer) carbon atom content, 10 at% or less, oxygen permeability, 0.1 cc / m ² / Day, water vapor transmission rate, 0.1 g / m ² / Day antireflection film is formed on TAC film, layer structure, silicon oxide film (third layer) / titanium oxide film (second layer) / silicon oxide film (first layer) / hard coat layer / TAC film An antireflection film according to the present invention was obtained.
The antireflection film according to the present invention obtained above is laminated not only on the surface of various display devices such as liquid crystal display devices, organic EL display devices, inorganic EL display devices, and PDPs, but also on the surfaces of flexible various display devices, Or it can be placed and used, and it can follow flexibly even if it is bent strongly, and it has excellent adhesion, and furthermore, even in a high temperature and high humidity atmosphere, it has optical functions such as anti-reflection and gas barrier properties. It was possible to maintain functions such as
(Experimental example)
Based on JIS K 5600-5-1, the antireflection film formed above is sandwiched between test plates so that the antireflection film surface is bent outward, and is bent at an angle of 180 degrees uniformly at the same speed over 2 seconds. After the bending test of the cylindrical mandrel method (mandrel diameter, 8 mm, bending time, 2 seconds), no film cracking or peeling was observed in the antireflection film, and the film was bent with a uniform and good film quality. In the oxygen transmission rate after the test and the water vapor transmission rate, the oxygen transmission rate was 0.2 cc / m. ² / Day, water vapor transmission rate, 0.3 g / m ² / Day, gas barrier properties were maintained, film cracking or peeling from the substrate was not observed, and the film was excellent in flexibility.
Comparative Example 1
As a flexible substrate (polymer film), a hard coat layer having a thickness of 6 μm is formed on a triacetyl cellulose film (product name: Fujitac, manufactured by Fuji Photo Film Co., Ltd., refractive index: 1.50) subjected to saponification treatment of 80 μm. What was formed was used. The refractive index of this hard coat layer was 1.51.
A reaction chamber a shown in FIG. 5 forms a titanium oxide film (first layer), a reaction chamber b forms a silicon oxide film (second layer), a reaction chamber c forms a titanium oxide film (third layer), and In the reaction chamber b, a four-layer antireflection layer was formed on the silicon oxide film (fourth layer) by sputtering.
Sputtering was performed by replacing the CVD electrode with a sputtering target.
A 13.56 MHz RF power source was used as the high frequency power source, and the feeding speed of the polymer film as the base material during continuous film formation was adjusted according to the film thickness of each layer. Other conditions are as follows.
<First Layer: Titanium Oxide Film Formation Conditions (Reaction Chamber a)>
Applied power 5kW
Target titanium
Introduced gas Argon, oxygen
Deposition pressure 0.5Pa
<Second Layer: Film Formation Conditions for Silicon Oxide Film (Reaction Chamber b)>
Applied power 5kW
Introduced gas Argon, oxygen
Deposition pressure 0.3Pa
<Third layer: Titanium oxide film formation conditions (reaction chamber a)>
Applied power 5kW
Target titanium
Introduced gas Argon, oxygen
Deposition pressure 0.5Pa
<Fourth layer: Conditions for forming silicon oxide film (reaction chamber c)>
Applied power 5kW
Introduced gas Argon, oxygen
Deposition pressure 0.3Pa
[0069]
The measurement results of the antireflection film (optical functional film) formed on the TAC film under the above conditions are shown below.
The apparatus used for the measurement of the antireflection film of Comparative Example 1 was also the same as that of Example 1.
<First layer: measurement result of titanium oxide film>
Film thickness 20nm
Film composition (Atomic%) Ti: C: O = 35: 2: 63
Refractive index (λ = 550 nm) 2.40
<Second layer: measurement result of silicon oxide film>
Film thickness 42nm
Film composition (Atomic%) Si: C: O = 35: 1: 64
Refractive index (λ = 550 nm) 1.46
<Third layer: measurement result of titanium oxide film>
Film thickness 33nm
Film composition (Atomic%) Ti: C: O = 35: 1: 63
<Fourth layer: measurement result of silicon oxide film>
Film thickness 110nm
Film composition (Atomic%) Si: C: O = 34: 1: 65
<Measurement result of antireflection film>
Layer structure: silicon oxide film / titanium oxide film / silicon oxide film / titanium oxide film
Oxygen permeability 0.2cc / m ² / Day (23 ° C., 0% Rh)
Water vapor transmission rate 0.2g / m ² / Day (38 ° C, 100% Rh)
Visibility reflectance 0.20%
[0075]
As shown in the results of the formation of the antireflection film described above, it has a luminous reflectance of 0.2%, an optical characteristic, a titanium oxide film (first layer), a silicon oxide film (second layer), and titanium oxide. Carbon atom content of film (third layer) and silicon oxide film (fourth layer), 10 at% or less, oxygen permeability, 0.2 cc / m ² / Day, water vapor transmission rate, 0.2 g / m ² / Day antireflection film is formed on the TAC film, layer structure, titanium oxide film (first layer) / silicon oxide film (second layer) / titanium oxide film (third layer) / silicon oxide film (fourth) Layer) / hard coat layer / TAC film of Comparative Example 1 was obtained.
(Experimental example)
Based on JIS K 5600-5-1, the antireflection film formed above is sandwiched between test plates so that the antireflection film surface is bent outward, and is bent at an angle of 180 degrees uniformly at the same speed over 2 seconds. After the bending test of the cylindrical mandrel method (mandrel diameter, 8 mm, bending time, 2 seconds), the oxygen transmission rate after the bending test and the water vapor transmission rate were 2.5 cc / m ² / Day, water vapor transmission rate, 3.0 g / m ² / Day, film cracking, peeling from the substrate, and poor gas barrier properties.
(Comparative Example 2)
A silicon oxide film (first layer) was formed in the reaction chamber a by the sputtering method using the apparatus of FIG.
Further, a titanium oxide film (second layer) is formed in the reaction chamber b, and a silicon oxide film (third layer) is formed in the reaction chamber c by plasma CVD.
<First Layer: Silicon Oxide Film Formation Conditions (Reaction Chamber a)>
Applied power 5kW
Introduced gas Argon, oxygen
Deposition pressure 0.3Pa
<Second Layer: Titanium Oxide Film Formation Conditions (Reaction Chamber b)>
Applied power 1kW
Oxygen gas flow rate 3000sccm
Titanium tetraisopropoxide gas flow rate 100sccm
Deposition pressure 6Pa
<Third Layer: Film Formation Conditions for Silicon Oxide Film (Reaction Chamber c)>
Applied power 1kW
Oxygen gas flow rate 3000sccm
Tetramethoxysilane gas flow rate 1000sccm
Deposition pressure 9Pa
[0081]
The measurement results of the antireflection film (optical functional film) formed on the TAC film under the above conditions are shown below.
The apparatus used for the measurement of the antireflection film of Comparative Example 2 was the same as that of Example 1.
<First layer: measurement result of silicon oxide film>
Film thickness 118nm
Film composition (Atomic%) Si: C: O = 38: 5: 57
Refractive index (λ = 550 nm) 1.70
<Second layer: measurement result of titanium oxide film>
Film thickness 20nm
Film composition (Atomic%) Ti: C: O = 35: 5: 60
Refractive index (λ = 550 nm) 2.21
<Third layer: measurement result of silicon oxide film>
Film thickness 120nm
Film composition (Atomic%) Si: C: O = 35: 1: 64
Refractive index (λ = 550 nm) 1.45
<Measurement result of antireflection film>
Layer structure: silicon oxide film / titanium oxide film / silicon oxide film
Oxygen permeability 0.2cc / m ² / Day (23 ° C., 0% Rh)
Water vapor transmission rate 0.1g / m ² / Day (38 ° C, 100% Rh)
Visibility reflectance 0.41%
[0086]
As shown in the results of the formation of the antireflection film described above, the optical reflectance is 0.41%, and the silicon oxide film (first layer), the titanium oxide film (second layer), and Carbon atom content of silicon oxide film (third layer), 10 at% or less, oxygen permeability, 0.2 cc / m ² / Day, water vapor transmission rate, 0.2 g / m ² / Day antireflection film is formed on TAC film, layer structure, silicon oxide film (first layer) / titanium oxide film (second layer) / silicon oxide film (third layer) / hard coat layer / TAC film Thus, an antireflection film of Comparative Example 2 was obtained.
(Experimental example)
The antireflection film formed above is sandwiched between test plates so that the antireflection film surface is bent outward based on JIS K 5600-5-1, and bent at an angle of 180 degrees uniformly at the same speed over 2 seconds. After the bending test of the cylindrical mandrel method (mandrel diameter, 8 mm, bending time, 2 seconds), the oxygen transmission rate after the bending test and the water vapor transmission rate were 2 cc / m. ² / Day, water vapor transmission rate, 2.0 g / m ² / Day, film cracking, peeling from the substrate, and poor gas barrier properties.
Moreover, as a result of visually observing the film, white turbidity was generated, the appearance was inferior, and the optical functionality, gas / gas barrier property, adhesion with image display, and adhesion were inferior.
[0088]
【The invention's effect】
As is apparent from the above description, the present invention provides an antireflection film in which an antireflection layer composed of a multilayer film having a different refractive index is formed on a flexible substrate directly or via another layer. In the antireflection layer, the layer on the substrate side is composed of a silicon oxide layer having an organic group containing 10 at% or more and 50 at% or less of carbon atoms, and on the layer on the substrate side, When an antireflection film comprising an inorganic oxide as a main component and containing at least one layer containing carbon atoms of 1 at% or more and 10 at% or less and having gas barrier properties and flexibility is produced, liquid crystal In addition to the surface of various display devices such as display devices, organic electroluminescence (hereinafter also referred to as “EL”) display devices, inorganic EL display devices, and plasma displays (hereinafter also referred to as “PDP”), flexible Laminated or placed on the surface of various display devices, it can follow flexibly even if it is bent strongly, has excellent adhesion, and is also anti-reflective in a hot and humid atmosphere. It is possible to maintain functions such as optical functionality and gas barrier properties.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing a layer structure which is an embodiment of an antireflection film for forming a multilayer antireflection film according to the present invention.
FIG. 2 is a schematic cross-sectional view showing a layer structure which is an embodiment of an antireflection film for forming a multilayer antireflection film according to the present invention.
FIG. 3 is a schematic cross-sectional view showing an example of a liquid crystal display device whose display surface is covered with a multilayer antireflection film according to the present invention.
FIG. 4 is a schematic view for explaining a method for producing an antireflection film according to the present invention by plasma CVD.
FIG. 5 is a schematic view for explaining a method for producing an antireflection film according to the present invention by plasma CVD.
[Explanation of symbols]
1, 21, 30 Polymer film (base material)
2,22 Substrate unwinding part
2 ', 26 Base material take-up part
3, 23 Vacuum container
4, a, b, c Reaction chamber
5, 27 Vacuum pump
6, a2, b2, c2 Source gas inlet
7, 7 'Reverse roll
8, 24 Drum for film formation
9, a1, b1, c1 electrodes
10 Power supply
11 Plasma
12 Anti-reflective coating
13 Substrate side layer (low refractive index layer made of carbon-containing silicon oxide)
14 Layer formed on the substrate side layer (layer made of inorganic oxide)
15 Outermost layer (low refractive index layer)
16 Intermediate layer (high refractive index layer)
25 Isolation wall
31 Hard coat layer
32 Silicon oxide layer
33 Titanium oxide layer
34 Carbon-containing silicon oxide layer
35 Antifouling layer
36 Antireflection film
37 TAC substrate film
38 Polarizing element
39 Liquid crystal display elements
40 Polarizing plate
41 Backlight unit

Claims (9)

In the antireflection film which forms the antireflection layer which consists of a multilayer film from which a refractive index differs directly or on another layer on a flexible substrate, a substrate side among the above-mentioned antireflection layers The layer comprises a silicon oxide layer having an organic group containing 10 atomic% or more and 50 atomic% or less of carbon atoms, and an inorganic oxide as a main component and carbon atoms of 1 atomic% on the substrate side layer. An antireflective film characterized by forming at least one layer containing 10 atomic% or less and having gas barrier properties and flexibility. 2. The reflection according to claim 1, wherein the layer on the substrate side has a refractive index in a range of 1.5 to 1.8 (wavelength λ = 550 nm), a film thickness of 5 nm to 300 nm. Prevention film. Of the layers formed on the substrate-side layer, the layer forming the outermost layer has a refractive index of 1.4 to 1.5 (wavelength λ = 550 nm), film thickness of 5 nm to 300 nm. The antireflection film according to claim 1, wherein the antireflection film is a silicon oxide layer in the range. In the layer formed on the substrate-side layer, an intermediate layer is provided between the outermost layer and the substrate-side layer, and the intermediate layer is a layer mainly composed of titanium oxide, or It is a layer mainly composed of ITO (indium / tin oxide) and has a refractive index in the range of 1.8 to 2.5 (wavelength λ = 550 nm), film thickness of 5 nm to 300 nm. The antireflection film according to any one of claims 1 to 3. The optical functional film according to claim 1, wherein the antireflection layer is formed by vacuum deposition, ion plating, sputtering, or plasma CVD. The antireflection film according to any one of claims 1 to 5, wherein a hard coat layer is provided. The antireflection film according to any one of claims 1 to 6, wherein an antifouling layer is laminated on the uppermost layer. An image display device, wherein the antireflection film according to claim 1 is laminated or disposed on the observation side of the display unit. An image display device, wherein the antireflection film according to claim 1 is laminated or arranged on the observation side of the flexible display unit.

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