JP2011203757A - Liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a liquid crystal display device having high wear resistance.SOLUTION: The liquid crystal display device includes a backlight unit, a backlight unit-side polarizing plate, and a liquid crystal cell held by two glass plates and having an electrode, a liquid crystal layer, an alignment layer, and a color filter disposed therein. A transparent front plate is arranged at a side of the liquid crystal cell opposite to the backlight unit, and a polarizing plate is stuck to the liquid crystal cell, and a transparent organic medium layer is arranged between the front plate and the liquid crystal cell. A bank is provided around the transparent organic medium layer, and an antireflection film is provided on the side of the front plate, not opposing to the transparent organic medium layer.

Description

  The present invention relates to a liquid crystal display device. Specifically, the present invention relates to a liquid crystal display device having a transparent front plate on an image display surface.

  In an image display device using liquid crystal, light from a light source is recognized as an image by passing through a liquid crystal layer, a color filter, a polarizing plate, and the like. In this case, the outermost surface of the personal computer monitor application or the liquid crystal television application is a polarizing plate, and an anti-glare film or an antireflection film provided with fine irregularities is formed on the polarizing plate surface in order to suppress surface reflection. The polarizing plate is a thin film made of triacetyl cellulose, and the pencil hardness of this film is about 2 to 3H.

  Also, among liquid crystal display devices, in the case of a mobile phone, the image display surface is provided with a transparent resin substrate such as an acrylic resin on a polarizing plate, assuming that it is constantly rubbed in clothes, and clothing etc. The structure is such that there is no direct contact.

  As mentioned above, the polarizing plate is a thin film made of triacetylcellulose, and the pencil hardness of this film is about 2 to 3H, but the surface has unevenness due to anti-glare treatment. Therefore, the abrasion resistance is lowered. Therefore, when wiping off the surface dirt with a rag or the like at home, if the foreign material having high hardness such as sand or earth adheres to the rag, it will be damaged. That is, it is a problem that the rubbing resistance is low when the outermost surface is a polarizing plate.

  Even if it is placed indoors, there is a risk that objects will hit the surface of a personal computer monitor or LCD TV. However, although the glass plate under the polarizing plate varies depending on the product, it is approximately 0.5 to 0.7 mm, so if the tableware, vase, toy, etc. collide, there is a possibility that it will break if the degree of impact is large. In the future, both personal computer monitors and LCD televisions will have larger screens. The larger the screen without changing the glass thickness, the lower the impact resistance, and even the smallest impacts are more likely to break.

  Furthermore, since the transparent resin substrate on the outermost surface of the mobile phone has a thickness of about 2 mm and is flat, even if it is placed in a pocket of the jacket, it is difficult to be damaged so as to reduce the visibility. However, since there is a gap with the polarizing plate, there is a problem that scenery is strongly reflected on the image display surface due to reflection on both sides of the substrate, and visibility in a bright place is lowered.

  In addition, in the manufacture of liquid crystal panels, the two glasses encapsulating liquid crystals are as thin as 0.5 to 0.7 mm, and the glass breaks if held stronger than necessary during the transport of each process or during wiring. There is a fear. Therefore, accuracy is required for holding during the manufacturing of the liquid crystal panel in the manufacturing apparatus.

  The present invention has been devised to solve these problems.

  As a result of studying various materials and substrate configurations, we have provided a transparent substrate on the outermost surface to improve abrasion resistance, and by filling a transparent organic medium between the polarizing plate and the transparent substrate, the air layer As a result, it was found that the reflection of the image can be suppressed by closing the cover.

  In addition, even when the front plate is an organic resin such as an acrylic plate, the present inventors have found that by providing an antireflection film mainly composed of high-hardness silica, the abrasion resistance can be improved.

  Further, by attaching the polarizing plate to the front plate, the present inventors have found an effect that the absorption axis of the polarizing plate can be adjusted by fine adjustment of the location of the front plate.

  In addition, the silica antireflection film has a lower contact angle to the liquid compared to the transparent substrate, that is, has high wettability, thus improving the adhesion of the polarizing plate and suppressing the generation of bubbles when filling a transparent organic medium. And found out that the present invention has been achieved.

  In addition, since the front plate is provided at the time of conveyance, even if the liquid crystal panel is held slightly strong, the panel itself is not easily damaged, and it is not necessary to increase the holding force accuracy of the holding system of the manufacturing apparatus.

  One means for achieving the above object is as follows.

(1) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged,
A transparent front plate on the side of the liquid crystal cell not facing the backlight unit;
And a polarizing plate is stuck on the liquid crystal cell,
A liquid crystal display device comprising a transparent organic medium layer between the front plate and the liquid crystal cell.

(2) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged,
A transparent front plate on the side of the liquid crystal cell not facing the backlight unit;
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
A liquid crystal display device, wherein a polarizing plate is attached to the transparent organic medium layer side of the front plate.

(3) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged,
A transparent front plate on the side of the liquid crystal cell not facing the backlight unit;
And a polarizing plate is stuck on the liquid crystal cell,
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
A liquid crystal display device comprising an antireflection film on a side of the front plate not facing the transparent organic medium layer.

(4) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged therein,
A transparent front plate on the side of the liquid crystal cell not facing the backlight unit;
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
And the polarizing plate is stuck on the medium layer side of the transparent organic matter of the front plate,
A liquid crystal display device comprising an antireflection film on a side of the front plate not facing the transparent organic medium layer.

(5) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged,
A transparent front plate having antireflection films on both sides on the side of the liquid crystal cell not facing the backlight unit;
And a polarizing plate is stuck on the liquid crystal cell,
A liquid crystal display device comprising a transparent organic medium layer between the front plate and the liquid crystal cell.

(6) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are disposed therein,
A transparent front plate having antireflection films on both sides on the side of the liquid crystal cell not facing the backlight unit;
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
A liquid crystal display device, wherein a polarizing plate is attached to the transparent organic medium layer side of the front plate.

(7) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell held by two glass substrates and having an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged therein,
A transparent front plate having an antireflection film on the side of the liquid crystal cell not facing the backlight unit;
And a polarizing plate is stuck on the liquid crystal cell,
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
The backlight, the liquid crystal cell, and the polarizing plate are held by a frame, and the front plate is bonded to the polarizing plate through the transparent organic medium layer.

(8) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged therein,
A transparent front plate having an antireflection film on the side of the liquid crystal cell not facing the backlight unit;
And a polarizing plate is stuck on the liquid crystal cell,
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
The backlight, the liquid crystal cell, the polarizing plate, the transparent organic medium layer, and the front plate are held by a frame.

(9) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell held by two glass substrates and having an electrode, a liquid crystal layer, an alignment layer, and a color filter are disposed therein,
A transparent front plate having an antireflection film on the side of the liquid crystal cell not facing the backlight unit;
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
And the polarizing plate is stuck on the medium layer side of the transparent organic matter of the front plate,
The liquid crystal display device is characterized in that the backlight and the liquid crystal cell are held by a frame, and the polarizing plate surface of the front plate is bonded to the liquid crystal cell via the transparent organic medium layer.

(10) In a liquid crystal display device in which a liquid crystal cell having an electrode, a liquid crystal layer, an alignment layer, and a color filter is arranged and held by a backlight unit, a polarizing plate on the backlight unit side, and two glass substrates.
A transparent front plate having an antireflection film on the side of the liquid crystal cell not facing the backlight unit;
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
And the polarizing plate is stuck on the medium layer side of the transparent organic matter of the front plate,
The backlight, the liquid crystal cell, the transparent organic medium layer, the polarizing plate, and the front plate are held by a frame.

(11) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged therein,
A transparent front plate having an antireflection film on the side of the liquid crystal cell not facing the backlight unit;
And a polarizing plate is stuck on the liquid crystal cell,
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
The backlight, the liquid crystal cell, and the polarizing plate are held by a frame, the front plate is bonded to the polarizing plate through the transparent organic medium layer, and the frame and the front plate are fixed. A liquid crystal display device.

(12) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell held by two glass substrates and having an electrode, a liquid crystal layer, an alignment layer, and a color filter are disposed therein,
A transparent front plate having an antireflection film on the side of the liquid crystal cell not facing the backlight unit;
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
And the polarizing plate is stuck on the medium layer side of the transparent organic matter of the front plate,
The backlight, the liquid crystal cell, and the polarizing plate on the backlight unit side are held by a frame, and the polarizing plate surface of the front plate is bonded to the liquid crystal cell via the transparent organic medium layer. A liquid crystal display device, wherein the frame and the front plate are fixed.

(13) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell held by two glass substrates and having an electrode, a liquid crystal layer, an alignment layer, and a color filter are disposed therein,
A transparent front plate having an antireflection film on the side of the liquid crystal cell not facing the backlight unit;
And a polarizing plate is stuck on the liquid crystal cell,
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
The backlight is held by a frame, the liquid crystal cell and the polarizing plate are held by a transparent organic medium layer, and the front plate is bonded to the polarizing plate through the transparent organic medium layer. A liquid crystal display device, wherein the frame and the front plate are fixed.

(14) In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged therein,
A transparent front plate having an antireflection film on the side of the liquid crystal cell not facing the backlight unit;
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
And the polarizing plate is stuck on the medium layer side of the transparent organic matter of the front plate,
The backlight is held by a frame, the liquid crystal cell and the polarizing plate on the backlight unit side are held by the transparent organic medium layer, and the polarizing plate surface of the front plate is the transparent organic medium layer. A liquid crystal display device, wherein the frame and the front plate are fixed to each other through the liquid crystal cell.

  (15) The liquid crystal display device according to any one of (1) to (14), wherein a driver of the liquid crystal cell is disposed below the liquid crystal cell.

  (16) The liquid crystal display device according to any one of (1) to (15), wherein the arithmetic average roughness (Ra) of the front plate is 10 nm or less.

  (17) The liquid crystal display device according to any one of (1) to (16), wherein a thickness of the transparent organic medium layer is 0.1 to 10 mm.

(18) When the refractive index of the constituent member of the transparent organic medium layer is n and the refractive index of the front plate is n ₀ , these refractive indexes follow the following formulas (1) to (17) The liquid crystal display device described.
n ₀ −0.2 <n <n ₀ +0.2

  (19) The liquid crystal display device according to any one of (1) to (18), wherein the transparent organic medium layer contains a compound having absorption in the visible region.

  (20) The liquid crystal display device according to any one of (1) to (19), wherein the compound having absorption in the visible region is a compound having uniaxial anisotropy.

(21) The antireflection film is formed of silicon oxide fine particles and a binder,
The liquid crystal display device according to any one of (3) to (20), wherein the antireflection film has a gap inside.

(22) The antireflection film is formed from silicon oxide fine particles and a silicon compound having a hydrolyzable residue,
The liquid crystal display device according to any one of (3) to (21), wherein the antireflection film has a gap inside.

  (23) The antireflection film has a layer formed of a compound having a perfluoropolyether chain, a perfluoroalkyl chain, or a fluoroalkyl chain on the surface thereof (3) to (22) Liquid crystal display device.

(24) A backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are disposed therein,
A transparent front plate on the side of the liquid crystal cell not facing the backlight unit;
And a polarizing plate is stuck on the liquid crystal cell,
And in the manufacturing method of the liquid crystal display device which has a transparent organic medium layer between the front plate and the liquid crystal cell,
A method for producing a liquid crystal display device, wherein the contact angle between the surface of the polarizing plate in contact with the transparent organic medium layer and the water on the surface of the front plate is 10 ° or less.

(25) A backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are disposed therein,
The liquid crystal cell has a front plate that is transparent on the side not facing the backlight unit and has an antireflection film on at least one side;
And a polarizing plate is stuck on the liquid crystal cell,
And in the manufacturing method of the liquid crystal display device which has a transparent organic medium layer between the front plate and the liquid crystal cell,
A method for producing a liquid crystal display device, wherein the contact angle between the surface of the polarizing plate in contact with the transparent organic medium layer and the water on the surface of the front plate is 10 ° or less.

(26) A backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are disposed therein,
A transparent front plate on the side of the liquid crystal cell not facing the backlight unit;
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
In addition, in the liquid crystal display device in which a polarizing plate is attached to the transparent organic medium layer side of the front plate,
A method for producing a liquid crystal display device, wherein the contact angle between the surface of the polarizing plate in contact with the transparent organic medium layer and the water on the surface of the liquid crystal cell is 10 ° or less.

(27) A backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell that is held by two glass substrates and has an electrode, a liquid crystal layer, an alignment layer, and a color filter are disposed therein,
A front plate transparent on at least one side of the liquid crystal cell not facing the backlight unit and having an antireflection film on at least one side, and a transparent organic medium layer between the liquid crystal cells;
In addition, in the liquid crystal display device in which a polarizing plate is attached to the transparent organic medium layer side of the front plate,
A method for producing a liquid crystal display device, wherein the contact angle between the surface of the polarizing plate in contact with the transparent organic medium layer and the water on the surface of the liquid crystal cell is 10 ° or less.

  It was shown that by providing the front plate on the polarizing plate through a transparent organic medium, the abrasion resistance was improved and the reflectance was reduced more than that of the front plate alone. Furthermore, it was shown that the reflectance is further reduced by providing an antireflection film. It was shown that by attaching the polarizing plate to the front plate, it is easy to align the polarizing plate.

1 is a schematic cross-sectional view (1) of a liquid crystal module of a liquid crystal display device of the present invention. 1 is a schematic cross-sectional view of a liquid crystal display device of the present invention. The liquid crystal module cross-sectional schematic diagram (2) of the liquid crystal display device of this invention. The liquid crystal module cross-sectional schematic diagram (3) of the liquid crystal display device of this invention. The liquid crystal module cross section schematic diagram (4) of the liquid crystal display device of this invention. The figure of the polarizing plate / liquid crystal cell / polarizing plate / backlight unit part of the liquid crystal display device of this invention. The figure of the polarizing plate / liquid crystal cell / polarizing plate / backlight unit / frame part of the liquid crystal display device of this invention. The figure of the polarizing plate / liquid crystal cell / polarizing plate / backlight unit part of the liquid crystal display device of this invention. The figure of the backlight unit part which consists of a polarizing plate / liquid crystal cell / polarizing plate / light emitting diode of the liquid crystal display device of this invention. 4 shows a structure of a light emitting diode of a backlight unit of a liquid crystal display device of the present invention. Sectional schematic diagram (5) of the liquid crystal display device of this invention. Sectional schematic diagram (6) of the liquid crystal display device of this invention. Sectional schematic diagram (7) of the liquid crystal display device of this invention. Sectional schematic diagram (8) of the liquid crystal display device of this invention. The schematic diagram of a transparent organic substance filling process in the case of liquid crystal display device manufacture of this invention. The schematic diagram of the transparent organic substance medium layer containing the layer thickness control particle | grains used by this invention. The outline of the formation method of the anti-reflective film used by this invention. The cross-sectional photograph of the antireflection film used in the present invention. Presence strength of antireflection film used in the present invention.

First, the outline of the present invention will be described. However, the present invention is not limited to specific examples as long as the gist of the invention is not exceeded.
[A] Configuration of Image Display Device of the Present Invention The configuration of the image display device of the present invention will be described with reference to FIGS.
(1) Outermost surface is a front plate In the case of a monitor of a personal computer or a liquid crystal television currently on the market, the transparent organic medium layer 1 and the front plate 2 shown in FIG. In FIG. 1A, the backlight unit 3 has a structure in which a polarizing plate 4, a liquid crystal cell 5, and a polarizing plate are stacked. A combination of these is called a liquid crystal module. The liquid crystal cell includes a liquid crystal layer and a color filter layer disposed between a pair of transparent glass substrates, an electrode structure for applying an electric field to the liquid crystal layer, and various insulating films. A liquid crystal module including a liquid crystal cell having such a configuration, a polarizing plate for changing optical characteristics, and a backlight unit as a light source and mounted with a driving IC driver is called a liquid crystal module. In this case, since the outermost surface is a polarizing plate, the abrasion resistance is low as described above.

  Accordingly, in the present invention, a front plate is provided as shown in FIG. Further, by filling the gap between the front plate and the polarizing plate with a transparent organic medium, reflection on the back side of the front plate is suppressed.

  Further, the polarizing plate between the liquid crystal cell and the transparent organic medium layer is attached to the liquid crystal cell at the time of manufacture. In this case, it is necessary to align the polarization axis with high accuracy. Moreover, once pasted, it cannot be pasted again. However, if it is attached to the front plate with rough accuracy as shown in FIG. 1B, there is an advantage that when the front plate is mounted, the polarization axis can be adjusted again when the front plate is fixed, and the accuracy can be improved. This can be done because there is no problem in image display even if the mounting position of the front plate itself is slightly shifted.

As shown in FIG. 2, the liquid crystal module 6 is mounted, and the power supply unit 7, the control system 8, the front outer frame 9, and the rear outer frame 10 are mounted to manufacture a liquid crystal display device. FIG. 2A shows an example in which the front plate has the same size as the liquid crystal cell, and FIG. 2B shows an example in which the front plate described later is larger than the liquid crystal cell. Note that (b) shows a case where there is no outer frame on the front surface, but even if there is, there is no problem in terms of function. The liquid crystal modules shown in FIGS. 3 to 5 and FIGS. 11 to 14 described later have the same configuration as the liquid crystal display device shown in FIG.
(2) Formation of antireflection film on front plate The difference between the refractive index of the front plate and the refractive index of air causes reflection. Therefore, the liquid crystal display device having the structure shown in FIG. 3A is one in which the antireflection film 11 is formed on the front plate to suppress the reflection and improve the visibility. However, it is necessary to ensure sufficient abrasion resistance, and in that respect, an antireflection film made of an inorganic oxide is suitable.

FIG. 3B shows a case where a polarizing plate is mounted on the front plate, and this effect is the same as that shown in FIG.
(3) Antireflection film formation on both sides of the front plate When forming an antireflection film by dip coating, flow coating or the like, an antireflection film is formed on both sides of the front plate unless a mask is used. When the front plate is made of resin, the wettability of the surface is low, so that it becomes difficult to fill the transparent organic medium. That is, it becomes easy for air bubbles to enter and it is difficult to escape. Therefore, an antireflection film made of an inorganic oxide has an effect of improving the wettability of the surface and promoting the filling of a transparent organic medium. Further, when the polarizing plate is attached, the higher the wettability, the better the adhesion of the polarizing plate. FIG. 4A shows an antireflection film provided on both sides of the front plate.

FIG. 4B shows a case where a polarizing plate is mounted on the front plate, and this effect is the same as that shown in FIG.
(4) Holding the liquid crystal module in the frame In the case of a monitor of a personal computer or a liquid crystal television currently on the market, the backlight unit, polarizing plate, liquid crystal cell, and polarizing plate in FIG. It is a liquid crystal module. A control system, a power source, an outer frame, and the like are attached to this to function as an image display device. Since the transparent organic medium layer and the front plate can be mounted after the liquid crystal module is manufactured, there is an advantage that it can be manufactured without changing the manufacturing process of the conventional liquid crystal module.

  FIG. 5B shows a case where a polarizing plate is attached to the front plate, and this effect is the same as that shown in FIG.

  Incidentally, the polarizing plate, the liquid crystal cell, and the backlight unit are shown in detail in FIGS. Here, the driving IC driver 13 is disposed below the liquid crystal cell and is connected by the FPC board 14. The backlight unit and the liquid crystal panel are accommodated in the housing 15 of the backlight unit and the liquid crystal panel. A reflective layer 16 is laid on the inner surface of the housing to reflect light emitted from the fluorescent tube 17 and function as much light as possible for image display. The light traveling from the fluorescent tube toward the image display surface first passes through the diffusion plate 18 to further diffuse the light. Thereafter, the light enters the liquid crystal cell after passing through an optical sheet such as the diffusion sheet 19 or the prism sheet 20. Here, the upper lid 21 of the housing is provided so that the liquid crystal cell does not move.

  Here, the driving IC driver functions as a drain. When the backlight is turned on for a long time, the liquid crystal panel is also heated by the heat generated at that time. Since the upper part of the liquid crystal panel is particularly heated, the temperature rises. At this time, if the driving IC driver is coupled to the upper portion, it is strongly heated, so that damage to elements due to heat increases, resulting in a decrease in durability of the panel. Even if the elements are not damaged, there is a possibility that the image is blurred when the heat is transferred to the liquid crystal cell and the temperature exceeds the operating temperature as the liquid crystal. Therefore, it is ideal to place the driving IC driver below the liquid crystal cell. However, when the driving IC driver is disposed below, when a conventional liquid crystal display device without a front plate is wiped with a wet cloth, water droplets are transmitted through the image display portion, that is, through the polarizing plate, to the driving IC. There is also the possibility of entering the driver and causing a short circuit. For this reason, considering the daily handling of the user, a certain degree of waterproofing effect is required to dispose the driving IC driver below the liquid crystal cell. By providing the front plate here, waterproofness is exhibited, and the driving IC driver can be arranged under the liquid crystal cell, and as a result, the driving IC driver and the liquid crystal panel can be extended in life. It becomes.

  FIG. 8 shows a different number and configuration of diffusion sheets, prism sheets and the like between the backlight, the polarizing plate, and the liquid crystal cell as compared with FIG. In designing the display device, a shape corresponding to the performance of the diffusion plate, the diffusibility of the backlight, or the like is appropriately selected from these configurations.

6 to 8 use a fluorescent tube for the backlight, FIG. 9 shows a configuration using the light emitting diode 22 (or sometimes described as LED). The structure of the light emitting diode is shown in FIG. The light emitting diode has a reflecting surface 24 around the light emitting portion 23. At the time of designing the display device, either a fluorescent tube or a light emitting diode, or a configuration to be used in combination is appropriately selected.
(5) Holding the frame from the backlight unit to the front plate In the case of a monitor or liquid crystal television set currently on the market, a liquid crystal module (from the backlight unit, polarizing plate, liquid crystal cell, and polarizing plate in FIG. 5A) Are collectively held in a frame), and a control system, a power source, an outer frame, and the like are attached to function as an image display device. As shown in FIG. 11 (a), the transparent organic medium layer and the front plate are held on the frame, so that there is an advantage that a personal computer monitor and a liquid crystal television can be manufactured without changing the manufacturing process of the conventional liquid crystal display device. .

FIG. 11B shows a case where a polarizing plate is attached to the front plate, and this effect is the same as that shown in FIG.
(6) Front plate and frame fixing In FIG. 11, the frame holds the front plate. For example, in the case of a 32-inch liquid crystal TV, if glass with a thickness of 2 mm is used for the front plate, the amount of the front plate alone is about 1.5 kg. When glass with a thickness of 3 mm is used, it is about 2.2 kg. Therefore, since the frame holds the front plate, it is necessary to use a thicker member than before. This leads to an increase in the weight of the liquid crystal TV, which is not preferable.

  Therefore, as shown in FIG. 12A, by fixing the front plate and the frame, not only the frame but also other members can be held together with the front plate, so that it is not necessary to make the frame thick. That is, there are advantages that the amount of use of the member and the cost can be reduced, and that the member is thin, so that the processing is easy.

FIG. 12B shows a case where a polarizing plate is attached to the front plate, and this effect is the same as that shown in FIG.
(7) Holding a polarizing plate and a liquid crystal cell with a transparent organic medium layer As shown in FIG. 13 (a) and FIG. 14 (a), a polarizing plate and a liquid crystal cell are held with a transparent organic medium layer. Is held by the front plate, the only member held by the frame is the backlight. Therefore, since the frame can be made thinner than the above (6), the amount of use of the member and the cost for that can be further reduced, and since the member is further thinned, there is an advantage that processing is easy.

FIGS. 13B and 14B show the case where the polarizing plate is mounted on the front plate, and this effect is the same as that shown in FIG. 1B of FIG.
[B] Configuration unit, member, etc. (1) Backlight unit The backlight unit is composed of a light source and an optical sheet. Examples of the light source include a cold cathode tube or an LED. Examples of the optical sheet include a light guide plate, a diffusion sheet, a prism sheet, and a reflective polarizing sheet.
(2) Polarizing plate The polarizing plate is a plate having a function of transmitting only light in a specific vibration direction. In the present invention, there is no particular limitation, and those used in ordinary liquid crystal display devices are used. Two sheets are used for one display device, and one is provided between the backlight unit and the liquid crystal layer. The remaining one has different parts as described above, but can perform its own function.
(3) Liquid crystal cell A liquid crystal cell is generally held in the order of a transparent electrode, an alignment layer, a liquid crystal layer, an alignment layer, and a color filter between two glass substrates. This configuration is assumed. Further, even if a part of the structure is changed, the liquid crystal display device of the present invention can be used as long as the same function can be achieved.
(4) Front plate The front plate is preferably a transparent plate having almost no absorption in the visible region and high abrasion resistance. In addition, even if the front plate member has a high hardness, if the surface is roughened, the surface convex portion will be rubbed strongly when rubbed with a sharp object or sandy cloth, and scratches will be caused. Cheap. As described above, triacetyl cellulose has a pencil hardness of 2H to 3H, but the surface has an arithmetic average roughness (Ra) of 150 to 500 nm due to the antiglare treatment, and thus is easily scratched.

  Considering this point, first, a glass plate having a pencil hardness of 9H or more, an acrylic plate having a pencil hardness of 2H, triacetyl cellulose having a pencil hardness of 2H to 3H, and the like are listed as the front plate member. Further, as described above, the surface irregularities are small and flat, specifically, the arithmetic average roughness (Ra) is 100 nm or less, preferably 10 nm or less.

  Although the thickness of the front plate varies depending on the size of the liquid crystal display portion, it is preferably 0.7 mm or more when the front plate is made of glass, and 1 mm or more when a resin such as acrylic is used. If the thickness is smaller than this, the front plate is deformed during manufacturing, and the deformation affects the flatness of the display surface of the product.

The size of the front plate may be larger than that of the transparent organic medium layer, the polarizing plate, the liquid crystal cell, and the backlight unit as shown in FIGS.
(5) Transparent organic medium The transparent organic medium is solid or liquid at room temperature as a property in the present invention.

  The closer the refractive index of the transparent organic medium is to that of the front plate and the polarizing plate, the lower the reflectance. The composition of the front plate described later includes glass (refractive index 1.50 to 1.54), acrylic (refractive index 1.49), PET (refractive index 1.56), polycarbonate (refractive index 1.59), and the like. .

Here, when the refractive index of the front plate is n ₀ and the refractive index of the transparent organic medium is n, the reflectance R at the interface between the front plate and the transparent organic medium can be obtained from the following formula.

R = {(n ₀ −n) / (n ₀ + n)} 2
When there is no transparent organic medium inside these front plates, that is, in the state of the air layer (refractive index 1.0), reflection of about 3.7 to 5.2% occurs at the interface with the air layer of the front plate. .

  Reflection is caused by the difference in refractive index between the front plate and air. Therefore, reflection can be suppressed by filling the air layer with a transparent medium having a refractive index close to that of the front plate instead of air.

  When exposed to direct sunlight, if the reflectance at the interface between the front plate and the transparent organic medium, which is about 3.7 to 5.2%, is reduced to about 0.5%, the visibility is considerably improved. From the above formula, the refractive index at which the reflectance of one surface is reduced to about 0.5% by filling a transparent organic medium is as shown in Table 1 below.

  From this table, it is shown that the difference in the refractive index of the transparent organic medium relative to the refractive index of the front plate is desirably 0.2 or less in order to reduce the reflectance to about 0.5%.

Therefore, when the refractive index of the front plate is n ₀ and the refractive index of the transparent organic medium is n, it is preferable to select the front plate and the transparent organic medium so that the following inequality is satisfied.

n ₀ −0.2 <n <n ₀ +0.2
Examples of the transparent organic medium include the following.

  Examples of the solid include a thermosetting resin and a photocurable resin that are polymerized by thermosetting and photocuring a monomer. Moreover, the thermoplastic resin which has already completed superposition | polymerization is also mentioned.

  The thermosetting resin and the photocurable resin can be filled with the monomer after filling the gap with the front plate and then cured by applying appropriate heat or light, thereby closing the gap. Examples of monomers of these resins include those that are polymerized using double bonds in the monomers, those that polymerize different monomers or polymers, those that are polymerized by a dehydration reaction, and dealcoholization reactions.

  Styrene, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, which are polymerized using double bonds in the monomer Examples include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, and dodecyl acrylate. A transparent organic medium layer is formed by using these alone or in combination. A transparent organic medium layer can also be formed by copolymerizing these with another polymer or monomer. Examples of the polymer to be used include polyacrylic acid and polyvinyl alcohol. In addition, as the monomer, ethylene glycol monopropylene having a glycidyl group at its terminal, such as ethylene glycol, propylene glycol, diethylene glycol, 1,3-dihydroxycyclobutane, 1,4-dihydroxycyclohexane, 1,5-dihydroxycyclooctane, etc., having a hydroxyl group in the molecule Examples thereof include glycidyl ether and ethylene glycol diglycidyl ether.

  As monomers and polymers to be polymerized by dehydration reaction, those having two or more hydroxyl groups, or glycidyl groups, two or more amino groups at the terminal, and two or more carboxyl groups or carboxylic acid anhydride structures at the terminals What has a polycondensation is mentioned. Those having a hydroxyl group at the end include those having a glycidyl group at the end, such as ethylene glycol, propylene glycol, diethylene glycol, 1,3-dihydroxycyclobutane, 1,4-dihydroxycyclohexane, 1,5-dihydroxycyclooctane, polyethylene glycol, etc. Examples thereof include ethylene glycol monoglycidyl ether and ethylene glycol diglycidyl ether. Examples of those having an amino group at the terminal include ethylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,4-diaminobenzene, 2,6-diaminonaphthalene, and melamine. Examples of those having a carboxyl group at the terminal include adipic acid, 1,3-phthalic acid, 1,4-phthalic acid, fumaric acid, maleic acid, trimellitic acid, and pyromellitic acid. Examples of those having a carboxylic anhydride structure at the terminal include maleic anhydride, phthalic anhydride, pyromellitic anhydride, and the like. Examples of the polymerized by the dealcoholization reaction include compounds having an alkoxysilane group and compounds having an alkoxytitanium group. Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethoxytrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane 1, 1-aminopropyltriethoxysilane, 1-chloropropyltriethoxysilane, 1-glycidylpropyltriethoxysilane, and the like.

  Further, by using a highly elastic material such as polyisobutylene, the transparent organic medium layer can also improve the shock absorbing effect against impact. The range of elasticity of the transparent organic medium layer is preferably 5 to 40 as measured by rubber hardness measurement standard JISK6253. A hardness of 10 to 30 is more preferable. If the hardness is less than 5, the reliability when the front plate is held on the liquid crystal surface device for a long time may be lowered. On the other hand, when the hardness exceeds 40, the shock absorbing effect tends to be reduced.

  Examples of the thermoplastic resin include polystyrene, styrene / acrylic resin, acrylic resin, polyester resin, polypropylene, polyisobutylene, and the like. These are liquefied and heated easily when heated to Tg or higher.

  When the transparent organic medium is liquid or when the monomer is liquid, the transparent organic medium is filled by the following method. First, a bank 25 is provided around a member (a front plate, a polarizing plate, or a liquid crystal cell) in contact with a transparent organic medium. In the transparent organic medium layers shown in FIGS. 1, 3 to 5 and FIGS. 11 to 14, a bank is provided when the transparent organic medium is a liquid, or when the monomer is a liquid. Next, after injecting a transparent organic medium, if air bubbles are present, remove the air bubbles by applying pressure, pressurizing / heating with a device such as an autoclave, vibrating with a vibrator, or sucking. To do. FIG. 15 shows a schematic diagram of the process.

  Further, in order to make it easier for bubbles to escape, it is preferable to improve the wettability of the portion that is touched by the transparent organic medium. Specific surfaces include a front plate, a polarizing plate, an antireflection film, and a contact surface with a transparent organic medium of the liquid crystal cell. When the wettability of the surface is improved, an organic medium that is more transparent than air is likely to adhere, and as a result, bubbles are easily removed. Considering the specific condition of wettability on the basis of water, the contact angle with water is preferably 20 ° or less. In this case, almost all organic substances can be filled with almost no bubbles. In order to more reliably suppress bubbles, the contact angle with water is preferably 10 ° or less.

  When the bank covers the image display surface, it is possible to prevent the edge of the image from being invisible by the bank by using a transparent member. If the bank does not cover the image display surface, it need not be transparent. In that case, a black bank is preferable in order to enhance the sharpness of the image.

  The size of the transparent organic medium layer may be larger than that of the polarizing plate or the liquid crystal cell as shown in FIGS.

  When the transparent organic medium is a liquid, the liquid is preferably a solvent having a relatively high boiling point so that it is not easily volatilized by the heat generated by the liquid crystal display device. For example, alcohol (6 or more carbon atoms), diol (ethylene glycol, propylene glycol, etc.), hydrocarbon (10 or more carbon atoms), ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ester, diethylene glycol monoalkyl ether, diethylene glycol Examples thereof include monoalkyl esters, monoalkyl ethers of triethylene glycol, and monoalkyl esters of triethylene glycol.

  In the case of a liquid, the thickness of the transparent organic medium layer is preferably at least 0.1 mm or more in order to ensure the accuracy in forming a bank or to easily remove bubbles. On the other hand, if it is too thick, particularly in the case of a liquid, the weight of the liquid increases, making it difficult to hold the bank. Therefore, 10 mm or less is desirable even if it is thick. In order to make the thickness constant, there is a method of using transparent particles (layer thickness control particles) 26 having substantially the same target diameter and diameter. The particles are placed in advance so as not to overlap in a gap to be filled with the transparent organic medium, and then the transparent organic medium is filled. This makes it possible to control the thickness of the transparent organic medium layer to a target thickness by the particles. This particle is described as a layer thickness control particle. A schematic diagram is shown in FIG.

  It is also possible to control the layer thickness by mixing and filling the layer thickness control particles in a transparent organic medium.

  In addition to this, after filling a transparent organic medium layer with a photocurable resin monomer in which a dye having absorption anisotropy is dissolved, when the monomer is cured by irradiating polarized light using a polarizer, By having an absorption axis, the transparent organic medium layer can function as an auxiliary polarizing plate, and light leakage in the black display of the liquid crystal can be reduced.

In addition, since the pigment used in the color filter scatters the light from the light source, there is a problem that the scattered light leaks when black is displayed and the contrast is lowered. However, the scattered light is scattered on the transparent organic medium layer. By containing the pigment | dye which absorbs, the fall of contrast can be suppressed. The liquid crystal display device is bluish in color when displaying black. This is because light leakage in the wavelength region of 400 to 450 nm is stronger than in other wavelength regions. Therefore, by containing a pigment that absorbs light of 400 to 450 nm in the transparent organic medium layer, a clear black display can be achieved by suppressing bluishness during black display. Note that not only the pigment but also inorganic or metal nanoparticles have an effect of absorbing light due to the quantum size effect.
(6) Antireflection film Since the antireflection film is located on the outermost surface of the image display surface of the liquid crystal display device, it is desired to have a high abrasion resistance. Therefore, the material structure is preferably an inorganic-centered member structure rather than an organic material. In addition, since it is placed in the air, a member that is not easily affected by oxidation by oxygen or has already been oxidized is suitable.

  The multilayer antireflection film is composed of zirconium oxide having a high refractive index (refractive index of about 2.1), magnesium fluoride having a low refractive index (refractive index of about 1.38), and silicon oxide having a refractive index therebetween ( And a refractive index of about 1.5). In this case, since the pencil hardness of the antireflection film is as high as about 8 to 9H when the front plate is made of glass, it is preferable because it has high scratch resistance practically.

  In the case of a single-layer antireflection film, the film must have a refractive index lower than that of the substrate. Such a film is preferably formed of an inorganic oxide having a high pencil hardness. In particular, among inorganic oxides, a silicon oxide having a relatively low refractive index or a silicon compound having a hydrolyzable group is used as a matrix, and the porous film is made porous. A silicon oxide film (having voids inside) is suitable. Of these, silica sol is preferred. The silicon oxide fine particles and the silica sol are dispersed and dissolved in water or an alcohol solvent. By applying a coating 27 for forming an antireflection film, which is a mixture of these, to the front plate and then heating it quickly, the solvent is rapidly vaporized to generate bubbles 28 inside the film. In this state, solidification is completed, and the antireflection film 30 is formed in a state where the voids 29 are held in the film. This is schematically shown in FIG.

  FIG. 18 shows a cross-sectional photograph of the antireflection film used in the present invention.

  The substrate is an acrylic plate. Carbon is formed thereon. Here, carbon is formed only in order to prevent the cross section from being broken when the cross section sample in the measurement is prepared, and the effect of the present invention is exhibited even if it does not exist. FIG. 17 confirms the presence of several voids in the antireflection film used in the present invention. Therefore, the refractive index of the film is lower than the refractive index of normal silicon oxide, which is about 1.5. The refractive index tends to decrease as the content of the silicon oxide fine particles increases.

  Since the size of the voids is indefinite, a gap of about 5 to 150 nm is confirmed when observed from the long axis. Moreover, in order to confirm that it is a space | gap, it measured about the existing intensity | strength of the element of a space | gap and the part which is not a space | gap. The result is shown in FIG.

  From FIG. 19, it can be seen that the voids have a lower abundance of carbon, oxygen, silicon, etc. than the non-voided portions. This also confirms the presence of voids. The refractive index can be controlled by changing the ratio of silicon oxide (refractive index: about 1.5) and voids (refractive index: about 1.0) that are the matrix of the film. Specifically, the refractive index decreases as the void ratio increases. The formation of voids can also be controlled by the boiling point of the solvent used since the vaporization of the solvent in the coating film during thermal curing contributes to void formation, and the thermosetting temperature after coating the substrate. Furthermore, although the tendency can be found in FIG. 8, a lot of voids are formed in a relatively upper part (portion close to the outermost surface) of the antireflection film. This is presumably because bubbles that started to form inside the paint on the substrate due to thermosetting, that is, heating, rose to the vicinity of the surface. Due to this property, when antireflection films having different thicknesses are formed using paints having the same composition, the refractive index tends to be lower as the film is thinner when the thermosetting conditions are the same. This is because many voids are easily formed near the surface. In order to form many voids not only in the vicinity of the surface but also in the interior, a method of forming an antireflection film used in the present invention in multiple layers can be mentioned. As a result, voids are formed not only in the vicinity of the surface but also in the interior, so that the physical strength of the film is further improved.

  As described above, the silica sol is cited as one of the silicon compounds having a hydrolyzable residue, and the production method of the antireflection film is shown. This is a substance that changes to silicon oxide by heating. Since the formed silicon oxide has high transparency, the light transmittance is high. Examples of the tetraalkoxysilane used for producing the silica sol include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetraisobutoxysilane, and tetrabutoxysilane. Other than this, a silicon compound having a chlorine group in place of the alkoxysilane group, such as silicon tetrachloride, may also be mentioned.

  Examples of the silicon compound having a hydrolyzable residue other than silica sol include compounds having an amino group, a chloro group, a mercapto group, etc. in addition to tetraalkoxysilane. Specifically, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc. Is mentioned.

  Examples of the inorganic oxide fine particles include colorless or white fine particles such as silicon oxide, aluminum oxide, titanium oxide, and cerium oxide. In terms of size, it is desirable that the minor axis of the particles be equal to or less than the average film thickness in order to improve the flatness of the film. Of these, silicon oxide having a relatively low refractive index (refractive index is about 1.5 to 1.7) and aluminum oxide (refractive index is about 1.7 to 1.9) and the like are preferable. In particular, silicon oxide fine particles having a low refractive index are more suitable.

  When the silicon oxide fine particles are spherical, the average particle diameter is desirably 190 nm or less so that visible light (wavelength: 380 to 760 nm) incident on the film is not scattered. Beyond this, incident light is scattered and the film appears cloudy, which may cause problems in application to displays. Even when the silicon oxide fine particles are chain-like, it is desirable that the thickness be 190 nm or less for the same reason as described above. In addition, the transparency improves as the particle diameter of the silicon oxide fine particles is smaller. Therefore, the average particle size is preferably 100 nm or less. In the present invention, the lower limit of the size of the silicon oxide fine particles is about 9 nm because of the available size, but if it is well dispersed in the film, there is no problem even if it is smaller than this.

  The target film thickness when forming the antireflection film is preferably 60 to 190 nm. Theoretically, the film thickness t is reflected when t = λ / 4n where n is the wavelength λ of the incident light and n is the medium on which the light is incident (the refractive index of the transparent substrate and the antireflection film of the present invention). The rate is minimized.

Incident light is in the visible light region (380 to 760 nm), and the refractive index of the medium is from air (refractive index is about 1.0) to a relatively high refractive index transparent glass substrate (refractive index is about 1.7). Considering the use range of the member, the desirable minimum film thickness is 380 / (4 × 1.7) = 56 nm. If the wavelength is less than 56 nm, the reflectance cannot be sufficiently affected when light in the visible light region is incident. In consideration of the film thickness distribution when the coating film is formed, it is desirable to aim for a minimum film thickness of 60 nm, which is slightly larger than 56 nm. On the other hand, the maximum film thickness is preferably 760 / (4 × 1.0) = 190 and 190 nm. From the above conditions, it is considered that the film thickness of the present invention is appropriately 60 to 190 nm.
(7) Liquid repellent layer Although the antireflective film used in the present invention is formed by thermosetting, the antifouling property of the surface is improved by forming a layer made of a fluorine-containing compound having liquid repellency. . However, the thickness of the layer made of a fluorine-containing compound having liquid repellency needs to be extremely thin so as not to reduce the antireflection effect of the formed antireflection film. Specifically, the influence on the reflectance can be avoided by setting the thickness of the antireflection film to less than 56 nm as described above.

In addition, the formation form of the layer which consists of a fluorine-containing compound which has liquid repellency has the following two types.
(Α) Coating film comprising a fluorine-containing compound having liquid repellency A method of forming a coating film comprising a fluorine-containing compound having liquid repellency, which exhibits liquid repellency by coating the surface with a coating film It is. However, since this coating film has high resistance, the surface resistance of the antireflection film increases, and as a result, dust such as dust tends to adhere. Further, since the hardness of the liquid-repellent film (low hardness compared to silicon oxide or the like) determines the pencil hardness of the surface, the abrasion resistance may be lowered. Examples of the material for forming this film include Cytop (manufactured by Asahi Glass Co., Ltd.), INT304VC (manufactured by INT Screen Co., Ltd.) and the like. These are diluted with a solvent, applied, and heated to volatilize the solvent, and in some cases, thermally cured to form a film.
(Β) A perfluoropolyether compound or a perfluoroalkyl compound is bonded. This is a method of bonding a perfluoropolyether compound having an alkoxysilane group that can be bonded to a hydroxyl group at the terminal or a perfluoroalkyl compound to an antireflection film. . Specifically, a compound as shown below is bonded to the antireflection film.

  In this case, the surface of the antireflection film is not completely covered, but a perfluoropolyether chain or a perfluoroalkyl chain grows like grass on the antireflection film. Since the surface of the antireflection film is not completely covered, the film does not have high resistance even after performing this method, and the pencil hardness of the film can be prevented from being lowered.

  Furthermore, by forming these perfluoropolyether chains or perfluoroalkyl chains on the surface, the lubricity of the surface is also improved. Therefore, physical damage of the surface due to rubbing can be alleviated and a surface having high abrasion resistance can be formed.

From the above, in addition to antifouling properties, low resistance of the surface can be maintained and abrasion resistance can be improved. When forming a liquid repellent layer, a perfluoropolyether compound having an alkoxysilane group at the terminal or a perfluoroalkyl is used. A method using compounds is advantageous. The liquid repellent and the liquid repellent film forming method are shown below.
(A) Liquid repellent agent Specific examples of the perfluoropolyether compound having an alkoxysilane group at the terminal or the perfluoroalkyl compound include the following compounds 1 to 12.

  Among these, the compounds 1-8 are obtained by performing the synthesis method shown below. Compounds 9-12 have the compound names 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyl, respectively. Trimethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane is marketed by Hydras Chemical. Another commercially available material is Daikin Industries, Ltd. OPTOOL DSX. In addition, compounds 1 to 4 have a perfluoropolyether fluorine chain, and the liquid repellent film formed from the compound having this fluorine chain does not repel even when immersed in engine oil or gasoline for a long period (1000 hours). There is a feature that the aqueous property hardly decreases (the amount of decrease is 5 ° or less), which is advantageous in terms of antifouling properties. These compounds are represented by the following general formula.

  When the compounds 5 to 12 are immersed in engine oil or gasoline for a long period (1000 hours), the contact angle with water decreases from before the immersion (about 110 °) to almost the same level as the contact angle of the substrate.

(Synthesis of Compound 1)
DuPont Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) was dissolved in 3M PF-5080 (100 parts by weight), thionyl chloride (20 parts by weight) was added thereto, and the mixture was stirred for 48. Reflux for hours. Thionyl chloride and PF-5080 are volatilized with an evaporator to obtain acid chloride (25 parts by weight) of Krytox 157FS-L. PF-5080 (100 parts by weight), Silaace S330 (3 parts by weight) manufactured by Chisso Corporation, and triethylamine (3 parts by weight) are added to this and stirred at room temperature for 20 hours. The reaction solution was filtered with Radiolight Fine Flow A manufactured by Showa Chemical Industry, and PF-5080 in the filtrate was volatilized with an evaporator to obtain Compound 1 (20 parts by weight).

(Synthesis of Compound 2)
Compound 2 (20 parts by weight) was obtained in the same manner as in the synthesis of Compound 1, except that Chisso Co., Ltd. Silaace S330 (3 parts by weight) was used instead of Chisso Co., Ltd. Silaace S360 (3 parts by weight).

(Synthesis of Compound 3)
Compound similar to the synthesis of Compound 1 except that Daikin Industries' demnum SH (average molecular weight 3500) (35 parts by weight) is used instead of DuPont Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) 3 (30 parts by weight) was obtained.

(Synthesis of Compound 4)
Instead of Chisso Co., Ltd. Silaace S330 (3 parts by weight), Chisso Co., Ltd. Silaace S360 was used, and DuPont's Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) was made by Daikin Industries Compound 4 (30 parts by weight) was obtained in the same manner as in the synthesis of Compound 1, except that demnam SH (average molecular weight 3500) (35 parts by weight) was used.

(Synthesis of Compound 5)
Compound 1 except that 7H-dodecafluoroheptanoic acid (molecular weight 346.006) (3.5 parts by weight) manufactured by Daikin Industries, Ltd. was used instead of DuPont's Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) In the same manner as in the synthesis of Compound 5 (3.5 parts by weight) was obtained.

(Synthesis of Compound 6)
Using 7H-dodecafluoroheptanoic acid (molecular weight 346.06) (3.5 parts by weight) manufactured by Daikin Industries, Ltd. instead of Crytox 157FS-L (average molecular weight 2500) (25 parts by weight) manufactured by DuPont, Chisso Corporation ) Compound 6 (3.5 parts by weight) was obtained in the same manner as in the synthesis of Compound 1 except that Chisso Corporation Silaace S320 (2 parts by weight) was used instead of Silaace S310 (2 parts by weight).

(Synthesis of Compound 7)
Compound except for using 9H-hexadecafluorononanoic acid (molecular weight 446.007) (4.5 parts by weight) manufactured by Daikin Industries, Ltd. instead of DuPont's Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) In the same manner as in the synthesis of 1, compound 7 (4.5 parts by weight) was obtained.

(Synthesis of Compound 8)
Instead of DuPont's Krytox 157FS-L (average molecular weight 200) (25 parts by weight), Daikin Industries, Ltd. 9H-hexadecafluorononansan (molecular weight 446.007) (4.5 parts by weight) was used. Compound 8 (4.5 parts by weight) was obtained in the same manner as the synthesis of Compound 1 except that Chisso Corporation Silaace S320 (2 parts by weight) was used instead of Silaace S310 (2 parts by weight).
(B) Liquid repellent film forming method The liquid repellent film forming method using a perfluoropolyether compound having an alkoxysilane group at the terminal or a perfluoroalkyl compound is as follows.

  First, a perfluoropolyether compound having an alkoxysilane group at the terminal or a perfluoroalkyl compound is dissolved in a solvent. The concentration varies depending on the coating method, but is generally about 0.01 to 1.0% by weight. Alkoxysilane groups are gradually hydrolyzed by moisture in the solvent or moisture that enters the solvent from the air, so the solvent should be dehydrated or one that is difficult to dissolve water, such as fluorine-based solvents It is desirable to do. Specific examples of the fluorine-based solvent include FC-72, FC-77, PF-5060, PF-5080, HFE-7100, HFE-7200, and DuPont Vertrel XF manufactured by 3M. In this way, a liquid in which the perfluoropolyether compound or perfluoroalkyl compound is dissolved (hereinafter referred to as a liquid repellent treatment agent) is prepared.

  Next, a liquid repellent treatment agent is applied to the surface of the antireflection film. As a coating method, a normal coating method such as dip coating or spin coating is used. Then heat. Heating is a condition necessary for the alkoxysilane residue to form a bond with a hydroxyl group or the like on the surface. The heating is usually completed for about 10 minutes at 120 ° C. and for about 30 minutes at 100 ° C. It is about 1 hour at 90 ° C. Although it proceeds at room temperature, it takes a considerable amount of time.

  Finally, the surface is rinsed with a fluorine-based solvent, and the excess liquid repellent is removed to complete the liquid repellent treatment. As the solvent used for the rinsing, the solvent presented in the description of the liquid repellent treatment agent can be used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

  Three liquid crystal modules having a structure in which a polarizing plate, a liquid crystal cell, and a polarizing plate are stacked on a backlight unit are manufactured. One of them is provided with a glass plate having a thickness of 2 mm as a front plate through polyisobutylene as a transparent organic medium. The polyisobutylene layer has a thickness of about 1 mm. The other sheet is not filled with polyisobutylene but is provided with a similar glass plate through an air layer. The remaining one remains the liquid crystal module.

  When the pencil hardness of these surfaces was measured at a load of 1 kg, the module having the front plate did not scratch the front plate when the 2H pencil was used, but the module without the front plate was damaged. Therefore, the pencil hardness of 2H can be secured by providing the front plate, and the abrasion resistance can be improved. When the pencil hardness when the front plate was provided using a higher hardness pencil was examined, it was 9H or more in both cases where a transparent organic medium was provided and not provided.

  When the module provided with the front plate was compared, the surface reflection was stronger when the polyisobutylene was not filled. As a result, the reflectance was about 8% when the polyisobutylene was not filled and about 4% when the polyisobutylene was filled. Therefore, it was shown that reflection can be suppressed by closing the gap between the front plate and the polarizing plate with polyisobutylene.

  The polyisobutylene layer was produced when the thickness was about 0.1 mm and when the thickness was 10 mm, both of which had a reflectance of about 4%.

  Three liquid crystal modules having a structure in which a polarizing plate, a liquid crystal cell, and a polarizing plate are stacked on a backlight unit are manufactured. Further, a control system, a power source, etc. are mounted on the liquid crystal module to produce an image display device. Of these two sets, the driving IC driver is mounted on the lower part of the liquid crystal cell, and the other set has the driving IC driver mounted on the upper part of the liquid crystal cell. In a liquid crystal display device in which a driving IC driver is set below the liquid crystal cell, a glass plate having a thickness of 2 mm is provided as a front plate through a polyisobutylene as a transparent organic medium in one set. The polyisobutylene layer has a thickness of about 1 mm.

  These three sets of liquid crystal display devices were used continuously in a room at 40 ° C. for 3 hours. Then, in the liquid crystal display device in which the driving IC driver is mounted on the upper part of the liquid crystal cell, image blurring near the driving IC driver coupling portion occurs.

  When the liquid crystal display device is used, the heat from the backlight heats the inside of the liquid crystal display device. Especially in the upper part, the degree of heating increases. The driving IC driver is also heated, and the heat is transmitted to the liquid crystal cell. In the case of a liquid crystal display device in which a driving IC driver is mounted on the upper part of the liquid crystal cell, since the heat transferred from the driving IC driver to the liquid crystal cell is heated to near the operating temperature as the liquid crystal, the liquid crystal does not exhibit liquid crystal properties. As a result, it is considered that image blur has occurred.

  Next, in order to remove the dust on the screen, a weak alkaline glass cleaner is sprayed on the screen, and then wiped with a rag. A liquid crystal display device with a driving IC driver set at the bottom of the liquid crystal cell is provided with a front plate. Some of the screens that are not displayed no longer display video. This phenomenon did not occur with the other two units. When examined, the sprayed glass cleaner fell on the screen or fell from the gap between the polarizing plate and the frame to the driving IC driver, and the driver was wet. For this reason, it is considered that the wiring of the driving IC driver is short-circuited, and as a result, a part of the screen does not display an image. A similar phenomenon occurred with water mixed with detergent instead of glass cleaner.

  From the above, in order to prevent image blurring due to long-term use in high-temperature rooms and also have liquid-proof properties that can withstand screen cleaning with liquids such as glass cleaners and detergent mixtures, a driving IC driver is installed at the bottom of the liquid crystal cell. It has been shown that a liquid crystal display device that is mounted and provided with a front plate is suitable.

  A double-sided tape with a width of 6 mm and a thickness of 1 mm was applied in the vicinity of the end on the polarizing plate side to form a transparent organic medium bank. The pencil hardness and the reflectance were examined in the same manner as in Example 1 except that triethylene glycol was filled as a transparent organic medium. The pencil hardness in the case where there was a front plate was 9H or more, and triethylene glycol was filled. The reflectance in this case was about 4%.

First, a method for forming an antireflection film on the front plate will be described.
(1) Preparation of anti-reflective coating Silica sol solution as binder (acidic phosphoric acid, solvent is water: ethanol = 1: 4, alkoxysilane polymer is contained 2.5% by weight) (3 parts by weight), oxidized as inorganic oxide fine particles Dispersion of silicon (particle size is 10 to 30 nm, solid content is 10% by weight) (12 parts by weight), and ethanol (60 parts by weight) is mixed with this to form an antireflection film (hereinafter reflective) Preventive paint) is prepared. The boiling point of this paint was 80 ° C.
(2) Antireflection film formation This coating is spin coated on a 2 mm thick glass plate as a front plate.

After application, the glass plate is immediately placed in a thermostat controlled at 160 ° C. and heated for 10 minutes. As a result, the silica sol is changed to silicon oxide, and the thermosetting is completed. Thus, a glass plate having an antireflection film formed on the surface is completed.
(3) Optical evaluation experiment When the film thickness and refractive index of the antireflection film formed on the glass plate were measured, they were 120 nm and 1.33, respectively. The visibility reflectance of the surface on which the antireflection film was formed was 1.5%. The film thickness and refractive index were measured using an ellipsometer (model DHA-OLX) manufactured by Mizojiri Optical Industry. The reflectance of the glass plate without the antireflection film was about 4% on one side, and it was confirmed that the film of the present invention has an antireflection function.

When the cross section of the formed antireflection film was observed with a TEM, voids having a size of 5 to 150 nm were confirmed as shown in FIG.
(4) Preparation of liquid crystal display device A liquid crystal display device using polyisobutylene as a transparent organic medium was prepared in the same manner as in Example 1 except that the front plate on which the antireflection film was formed was used.
(5) Evaluation of pencil hardness, etc. When the pencil hardness was examined in the same manner as in Example 1, the pencil hardness of the front plate provided with the antireflection film was 6H, and when the front plate was not provided, that is, the outermost surface was a polarizing plate. In the case of (H), the improvement was confirmed.

  Moreover, the reflectance was 1.5%, and it was confirmed that the reflectance reduction effect was improved as compared with the front plate alone.

  An antireflection film was formed on both surfaces of the front plate in the same manner as in Example 4 except that the film was formed by dip coating instead of spin coating when forming the antireflection film. A liquid crystal display device was produced using polyisobutylene as a transparent organic medium in the same manner as in Example 4. At that time, in the case where the antireflection film was provided on both sides, the generation of bubbles was considerably less than in the case where the antireflection film was not provided, and the production was easy. This is because the antireflection film has voids inside and the wettability as the film is improved, so that it can be filled with almost no bubbles.

  Therefore, it was shown that the use of a front plate provided with antireflection films on both sides facilitates the production of a liquid crystal display device.

  When preparing an antireflection coating, N- (2-aminoethyl) -3-aminopropyltriethoxysilane (S320 manufactured by Chisso) (0.1 part by weight) is used instead of the silica sol solution (3 parts by weight). Prepare an antireflection coating in the same manner as in Example 5. After forming an antireflection film on the front plate using this paint, a liquid crystal display device was produced using polyisobutylene as a transparent organic medium in the same manner as in Example 1.

  The pencil hardness of the image display surface of this device was 4H, and the reflectance of the surface was 1.6%, which showed that it had higher abrasion resistance than the conventional one.

  A transparent organic medium disposed between the polarizing plate disposed on the viewer side of the liquid crystal panel and the front plate on which the antireflection film is formed on the viewer side, contains 0.1 wt% of the dye NK3981 (produced by Hayashibara Bioscience Institute). The acrylic resin monomer was cured by irradiating 365 nm light with a high-pressure mercury lamp in the same manner as in Example 1 except that the photocurable acrylic resin monomer solution was used.

  In the configuration of this example, the transparent organic medium acts as a spectral absorption layer having an absorption peak near a wavelength of 490 nm due to the effect of the mixed dye. Thereby, the contrast ratio improvement effect can be further expected.

  Color filters used in liquid crystal panels have blue, green, and red colored layers formed of organic pigments. For example, PB15: 6 + PV23 for blue, PG36 + PY150 for green, and PR177 + PY83 for red are known. Organic pigments exist in a state of being dispersed in the base polymer with a particle size of about 50 nm to 200 nm. However, since these are particle systems in the Rayleigh scattering region, the incident light from the light source arranged on the back of the liquid crystal panel is scattered. The scattered light becomes light leakage in black display, and the contrast ratio is lowered. In a liquid crystal display device, since the viewing angle characteristic is maintained, diffused light is incident on the liquid crystal panel instead of parallel light, and this influence is serious.

  At this time, since the scattered light of the color filter is due to Rayleigh scattering, it has a peak at a shorter wavelength than the original spectral characteristics. In particular, in the case of the green filter, the peak wavelength shifts from 530 nm to around 490 nm for a short wavelength, so that the light emission of the light source is in a wavelength region where the light emission is relatively large and the visibility is relatively high. A large impact. For example, if the light source is a narrow-band light emitting phosphor, the green phosphor has a secondary light emission in the vicinity of 490 nm. That is, in black display, light of 490 nm is specifically strengthened.

  In this embodiment, the transparent organic medium has an action of absorbing light at around 490 nm, but this makes it possible to absorb unnecessary light at around 490 nm that is specifically emphasized in black display. Since the light intensity near 490 nm is very weak in white display, absorption of this wavelength does not significantly affect the transmitted light intensity in white display, so that an effect of improving the contrast ratio can be obtained. In the configuration of this example, by adding 0.1 wt% of the dye, the black display transmittance could be reduced by -13%, and the contrast ratio could be improved by 10%.

  In order to function as a spectral absorption layer, any dye that has an absorption peak near 490 nm and can be dispersed in a transparent organic medium may be used, and it goes without saying that the present invention is not limited to this example. The addition amount of the dye may be optimized as appropriate in consideration of the absorbance of the dye used and the transmittance of black display and white display.

  This example is the same as Example 6 except that the substantially transparent organic medium is replaced with a photocurable acrylic resin to which 0.2 wt% of metal nanoparticles are added. This makes it possible to absorb specific light around 490 nm scattered by the color filter pigment in black display, and an effect of improving the contrast ratio can be obtained. Further, by treating the surface of the metal nanoparticles with a surfactant, the nanoparticles can be prevented from agglomerating and uniformly dispersed in the organic medium. In the configuration of this example, 0.2 wt% of gold nanoparticles having a particle size of 10 nm or less, which was surface-treated using, for example, a long-chain alkylthiol having an acrylic group as a surfactant, was added and mixed, so that the black transmittance was increased. -10% could be reduced, and the contrast could be improved by 8%.

  The metal nanoparticles have an absorption peak near 490 nm and can be dispersed uniformly in an organic medium by treating the surface. Nanoparticles made of various metal alloys are also used. Needless to say, the present invention is not limited to this embodiment. The addition amount of the nanoparticles may be optimized as appropriate in consideration of the absorption coefficient of the particles to be used and the transmittance for black display and white display.

In this example, the transparent organic medium was replaced with a photocurable acrylic resin to which 0.1 wt% of 4-carboxymethylazobenzene was added, and the light irradiation process during curing was changed, and this was the same as in Example 7. It is. In order to develop absorption anisotropy before photocuring treatment of the acrylic resin, a high pressure mercury lamp is used as a light source, i-line of 365 nm is taken out through an interference filter, and a pile polarizer having a quartz substrate laminated thereon is formed. Used as a linearly polarized light having a polarization ratio of about 10: 1, irradiation was performed substantially perpendicular to the substrate with an irradiation energy of about 5 J / cm ² . The polarization direction of the irradiated polarized light was the short side direction of the substrate. Thereafter, the front surface was irradiated with ultraviolet rays in the range of 250 to 450 nm for curing the acrylic resin, which is a transparent organic medium. These lights can be irradiated together. As a result, the transparent organic medium exhibited an absorption axis in the long side direction of the substrate. This is because the polarizing plate on the front surface of the liquid crystal panel used in this example, that is, the same direction as the absorption axis of the polarizing plate disposed on the viewer side. If the absorption axis of the front polarizing plate of the liquid crystal panel to be used is the short side direction, the irradiated polarization plane may be the long side direction of the substrate. In this embodiment, a material that exhibits an absorption axis in a direction orthogonal to the polarization direction of the polarized light irradiated is used. For example, the absorption axis is irradiated such that photooxidation occurs in the polarization direction of the polarized light irradiated. When using a material that has the same direction as the polarization plane of the polarized light, the direction of polarization to be irradiated may be changed. In addition, the same effect will be acquired if it is a photofunctional substance which expresses uniaxial absorption anisotropy by polarized ultraviolet irradiation, and it is not limited to the compound of a present Example. The amount to be added may be optimized as appropriate according to the anisotropic expression of the photofunctional substance to be used.

  Since the transparent organic medium in the present example functions as an auxiliary polarizing plate of the polarizing plate on the viewer side, even a slight uniaxial absorption anisotropy can effectively reduce light leakage in black display, The contrast ratio can be improved. In this example, the luminance of black display could be reduced by 5%, and the contrast ratio could be improved by 5%.

  This example is the same as Example 8, except that the transparent organic medium is replaced with a photocurable acrylic resin to which 0.12 wt% of direct orange 39 is added. The transparent organic medium in this example exhibits dichroism at a wavelength of 400 to 500 nm. Therefore, it is possible to efficiently absorb light leakage in a short wavelength region where the intensity is high in black display, and there is almost no influence on the white display, so that it is possible to improve the contrast ratio and correct the color tone of the black display. . In addition, the pigment | dye to add is a pigment | dye which shows dichroism, Comprising: What is necessary is just a pigment | dye which can be added to a transparent organic substance medium.

  In general, in a liquid crystal display device, the color tone of black display is more bluish than the color tone of white display. This is because the polarization degree of polarization is dependent on the wavelength, and light leakage becomes stronger in the wavelength range of 400 to 450 nm in black display. The transparent organic medium containing the dichroic dye of this example was able to absorb light leakage from 400 to 450 nm in black display. The color tone of black display was closer to an achromatic color, and the contrast ratio was improved by 3%.

  A liquid crystal display device was produced in the same manner as in Example 4 except that an acrylic plate having a thickness of 2 mm was used instead of the glass plate having a thickness of 2 mm.

  As a result, the thickness and refractive index of the antireflection film on the acrylic plate surface were 115 nm and 1.33, respectively. The visibility reflectance of the antireflection film-formed surface was 1.5%. When an acrylic plate not formed with an antireflection film is used, the reflectivity is about 4%. Therefore, the effect of reducing the reflectivity was confirmed as compared with the front plate alone.

  When the pencil hardness was examined, it was 4H. That is, it was shown that the hardness was improved as compared with the polarizing plate (H). Further, it was shown that the hardness was improved even in the case of the acrylic plate (2H) in which the antireflection film was not formed.

  Similar results were obtained when a photocurable acrylic resin was used instead of polyisobutylene as the transparent organic medium. Since the monomer of the photocurable acrylic resin to be used fills the acrylic plate while slightly dissolving the acrylic plate, there is a tendency that bubbles are not generated in the transparent organic medium layer.

  A liquid crystal display device was produced in the same manner as in Example 4 except that a 2 mm thick polycarbonate plate was used instead of the 2 mm thick glass plate.

  As a result, the film thickness and refractive index of the antireflection film on the polycarbonate plate surface were 115 nm and 1.33, respectively. The visibility reflectance of the antireflection film-formed surface was 1.5%. When a polycarbonate plate not formed with an antireflection film was used, the reflectivity was about 4%, so that the effect of reducing the reflectivity was confirmed compared to the front plate alone.

  When the pencil hardness was examined, it was 3H. That is, it was shown that the hardness was improved as compared with the polarizing plate (H). Further, it was shown that the hardness was improved even in the case of the polycarbonate plate not formed with the antireflection film (2B).

  Similar results were obtained when a photocurable acrylic resin was used instead of polyisobutylene as the transparent organic medium. Since the monomer of the photocurable acrylic resin used filled the polycarbonate plate while slightly dissolving it, there was a tendency that bubbles were not generated in the transparent organic medium layer.

A liquid repellent treatment is performed on the front plate formed with the antireflection film prepared in Example 4.
(1) Preparation of liquid repellent treatment solution First, a 0.5% by weight solution of compounds 1-12 (solvent: Fluorinert PF-5080 manufactured by 3M) is prepared. These are referred to as a liquid repellent treatment liquid. Further, a 0.1 wt% PF-5080 solution of Compound 1 is a liquid repellent treatment liquid [1], a 0.1 wt% PF-5080 solution of Compound 2 is a liquid repellent treatment liquid [2],. A 1 wt% PF-5080 solution is designated as a liquid repellent treatment liquid [12].

Next, for comparison, a 0.1% solution of Cytop CTX-109A manufactured by Asahi Glass Co., Ltd. was used as the liquid repellent treatment [13].
(2) When using the liquid-repellent treatment method / liquid-repellent treatment liquids [1] to [12] The liquid-repellent treatment liquid is applied with a brush. Next, the interior is left in a constant temperature bath heated to 95 ° C. for 30 minutes. The processing is completed by taking out the front plate, rinsing the surface with PF-5080, and removing excess liquid repellent treatment liquid.
-When using the liquid repellent treatment liquid [13] Apply the liquid repellent treatment liquid with a brush. Next, the inside is left for 90 minutes in a thermostatic oven heated to 95 ° C. The front plate is removed and the process is complete.
(3) Evaluation of liquid repellency The liquid repellency of the surface of the substrate after the liquid repellency treatment was evaluated by the contact angle with water. The results are shown in Table 2.

  The contact angle with water before the liquid repellent treatment, the refractive index and the reflectance before and after the liquid repellent treatment, and the pencil hardness are also shown.

  Before the liquid-repellent treatment, the antireflection film had a contact angle with water of less than 10 °. However, the contact angle became large in any film by the liquid repellent treatment. Since the refractive index and the reflectance did not change before and after the liquid repellent treatment, it was shown that the liquid repellent treatment does not deteriorate the performance related to these.

  However, those treated with a 0.1% solution of Cytop CTX-109A increased the surface resistance of the front plate. This is because Cytop CTX-109A almost completely covers the surface of the antireflection film, whereas compounds 1 to 12 have liquid repellent fluorine-based chains attached to the antireflection film surface through alkoxysilane groups. Therefore, as a result, it is considered that the antireflection film is not completely covered. As the film resistance increases, the resulting film is easily charged, so that there is a problem that dust and dust are likely to adhere. Therefore, compounds 1 to 12 that do not increase the film resistance are less likely to adhere dust and dust to the film. Is preferable in that it can be maintained.

  From the above, it was shown that a fluorine-based compound having an alkoxysilane group at the terminal is preferable in that the film resistance is not increased even when liquid repellency is imparted.

  Next, looking at the pencil hardness of the antireflection film, the films treated with compounds 1-12 for the liquid repellency all had a pencil hardness of 7H, while those treated with Cytop CTX-109A had a pencil hardness of H. Met. Since it was 6H before the liquid-repellent treatment, it was revealed that the liquid-repellent treatment using compounds 1 to 12 also improved the abrasion resistance.

  When compared with the compounds used in the liquid repellent treatment, the contact angle tended to be high when compounds 1 to 4 were used, and at least 110 ° when treated with compound 1 or 2. In particular, when compounds 3 and 4 were used, the contact angle was high, and in all cases a contact angle of 115 ° was shown. Compounds 1 to 4 are compounds having a perfluoropolyether chain, and others are compounds having a perfluoroalkyl chain or a fluoroalkyl chain. From this, it was shown that a liquid-repellent treatment with a compound having a perfluoropolyether chain can form a front plate with excellent liquid repellency.

  DESCRIPTION OF SYMBOLS 1 Organic substance medium layer, 2 Front plate, 3 Backlight unit, 4 Polarizing plate, 5 Liquid crystal cell, 6 Liquid crystal module, 7 Power supply unit, 8 Control system, 9 Front outer frame, 10 Rear outer frame, 11, 30 Antireflection film, 12 frame, 13 driving IC driver, 14 FPC board, 15 backlight unit and liquid crystal panel housing, 16 reflection layer, 17 fluorescent tube, 18 diffusion plate, 19 diffusion sheet, 20 prism sheet, 21 housing Top cover, 22 Light-emitting diode, 23 Light-emitting part, 24 Reflecting surface, 25 banks, 26 Layer thickness control particles, 27 Anti-reflective coating, 28 Air bubbles, 29 Air gaps.

Claims (20)

In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell held by two glass substrates and having an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged,
A transparent front plate on the side of the liquid crystal cell not facing the backlight unit;
And a polarizing plate is stuck on the liquid crystal cell,
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
A bank is provided around the transparent organic medium layer,
A liquid crystal display device comprising an antireflection film on a side of the front plate not facing the transparent organic medium layer. In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell held by two glass substrates and having an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged,
A transparent front plate on the side of the liquid crystal cell not facing the backlight unit;
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
A bank is provided around the transparent organic medium layer,
And the polarizing plate is stuck on the medium layer side of the transparent organic matter of the front plate,
A liquid crystal display device comprising an antireflection film on a side of the front plate not facing the transparent organic medium layer. In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell held by two glass substrates and having an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged,
A transparent front plate having antireflection films on both sides on the side of the liquid crystal cell not facing the backlight unit;
And a polarizing plate is stuck on the liquid crystal cell,
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
A bank is provided around the transparent organic medium layer,
A liquid crystal display device characterized by the above. In a liquid crystal display device in which a backlight unit, a polarizing plate on the backlight unit side, a liquid crystal cell held by two glass substrates and having an electrode, a liquid crystal layer, an alignment layer, and a color filter are arranged,
A transparent front plate having antireflection films on both sides on the side of the liquid crystal cell not facing the backlight unit;
And having a transparent organic medium layer between the front plate and the liquid crystal cell,
A bank is provided around the transparent organic medium layer,
A liquid crystal display device, wherein a polarizing plate is attached to the transparent organic medium layer side of the front plate. The backlight, the liquid crystal cell, and the polarizing plate are held by a frame, and the front plate is bonded to the polarizing plate through the transparent organic medium layer.
The liquid crystal display device according to claim 1. The backlight, the liquid crystal cell, the polarizing plate, the transparent organic medium layer, and the front plate are held by a frame.
The liquid crystal display device according to claim 1, wherein the liquid crystal display device is a liquid crystal display device. The backlight, the liquid crystal cell is held by a frame, and the polarizing plate surface of the front plate is bonded to the liquid crystal cell via the transparent organic medium layer.
The liquid crystal display device according to claim 2. The frame and the front plate are fixed,
The liquid crystal display device according to claim 5. The backlight, the liquid crystal cell, and the polarizing plate on the backlight unit side are held by a frame, and the polarizing plate surface of the front plate is bonded to the liquid crystal cell via the transparent organic medium layer, And the frame and the front plate are fixed,
The liquid crystal display device according to claim 2. The backlight is held by a frame, the liquid crystal cell, the polarizing plate is held by a transparent organic medium layer, and the front plate is bonded to the polarizing plate via the transparent organic medium layer, And the frame and the front plate are fixed,
The liquid crystal display device according to claim 1. The backlight is held by a frame, the liquid crystal cell and the polarizing plate on the backlight unit side are held by the transparent organic medium layer, and the polarizing plate surface of the front plate is the transparent organic medium layer. Are bonded to the liquid crystal cell, and the frame and the front plate are fixed.
The liquid crystal display device according to claim 2.   The liquid crystal display device according to claim 1, wherein a driver of the liquid crystal cell is disposed below the liquid crystal cell.   The liquid crystal display device according to claim 1, wherein an arithmetic average roughness (Ra) of the front plate is 10 nm or less.   14. The liquid crystal display device according to claim 1, wherein a thickness of the transparent organic medium layer is 0.1 to 10 mm. The refractive index of the constituent member of the transparent organic medium layer is n and the refractive index of the front plate is n _0. The liquid crystal display device described.
n ₀ −0.2 <n <n ₀ +0.2   The liquid crystal display device according to claim 1, wherein the transparent organic medium layer contains a compound having absorption in a visible region.   The liquid crystal display device according to claim 1, wherein the compound having absorption in the visible region is a compound having uniaxial anisotropy. The antireflection film is formed from silicon oxide fine particles and a binder,
The liquid crystal display device according to claim 1, wherein the antireflection film has a gap inside. The antireflection film is formed from silicon oxide fine particles and a silicon compound having a hydrolyzable residue,
The liquid crystal display device according to claim 1, wherein the antireflection film has a gap inside.   20. The antireflection film has a layer formed of a compound having a perfluoropolyether chain, a perfluoroalkyl chain, or a fluoroalkyl chain on the surface thereof. Liquid crystal display device.

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