JP2003232921A - Roll type circularly polarizing plate, roll type liquid crystal cell substrate and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a circularly polarizing plate which can be easily manufactured. <P>SOLUTION: A quarter-wave plate comprising a roll type polymer film is laminated with a roll type linearly polarizing film. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a circularly polarizing plate in which a λ / 4 plate made of a polymer film and a linear polarizing film are laminated. The present invention also relates to a liquid crystal cell substrate having a function as a circularly polarizing plate. Furthermore, the present invention also relates to a reflective or semi-transmissive liquid crystal display device having a circularly polarizing plate.

[0002]

2. Description of the Related Art Circular polarizing plates are used in various optical devices such as liquid crystal display devices. Circular polarizing plate is λ / 4
It is manufactured by laminating a plate and a linear polarizing plate. λ /
The four plates and the linear polarizing plate are arranged so that the angle between the slow axis of the λ / 4 plate and the transmission axis of the linear polarizing film is substantially 45 °. The circularly polarizing plate is generally obtained by punching out a chip having a shape corresponding to a liquid crystal cell from a λ / 4 plate and a linear polarizing film (both of which are usually roll-shaped films), and bonding the two while adjusting the angle. To manufacture.

[0003]

The conventional circularly polarizing plate has a large loss (low yield) when punching a chip from a λ / 4 plate and a linearly polarizing film, so that a large-sized circularly polarizing plate is obtained. However, it is difficult to adjust the angle in bonding the λ / 4 plate chip and the linear polarizing film chip.

An object of the present invention is to provide a circularly polarizing plate which is easy to manufacture. Another object of the present invention is to provide a liquid crystal cell substrate that is lightweight and thin, has flexibility, and is not easily damaged. Another object of the present invention is to provide a reflective or semi-transmissive liquid crystal display device suitable for carrying.

[0005]

The object of the present invention is to provide a rolled circularly polarizing plate of the following (1) to (4), the following (5),
The roll-shaped liquid crystal cell substrate of (6) and the following (7) to (1)
This is achieved by the liquid crystal display device of 1). (1) A λ / 4 plate made of a roll-shaped polymer film,
A roll-shaped circularly polarizing plate in which a roll-shaped linearly polarizing film is laminated.

(2) The longitudinal direction of the roll-shaped circularly polarizing plate and λ /
The roll-shaped circle according to (1), wherein the angle with the slow axis of the four plates is substantially 45 °, and the width direction of the roll-shaped circularly polarizing plate and the transmission axis of the linear polarizing film are substantially parallel. Polarizer. (3) The angle between the longitudinal direction of the roll-shaped circularly polarizing plate and the transmission axis of the linear polarizing film is substantially 45 °, and the longitudinal direction of the rolled circularly polarizing plate and the slow axis of the λ / 4 plate are substantially. Circularly polarizing plate according to (1), which are substantially parallel to each other. (4) A λ / 4 plate made of a roll-shaped polymer film,
It has a retardation value measured at a wavelength of 450 nm in the range of 60 to 135 nm, a retardation value measured at a wavelength of 590 nm in the range of 100 to 170 nm, and a retardation value measured at a wavelength of 450 nm from a retardation value measured at a wavelength of 590 nm. The rolled circularly polarizing plate according to claim 1, wherein a value obtained by subtracting the retardation value is 2 nm or more.

(5) A roll-shaped liquid crystal cell substrate in which a λ / 4 plate made of a roll-shaped polymer film and a roll-shaped linear polarization film are laminated, and the lengthwise direction of the roll-shaped liquid crystal cell substrate is λ / 4. The angle with the slow axis of the plate is substantially 45 °
And the width direction of the roll-shaped liquid crystal cell substrate and the transmission axis of the linear polarizing film are substantially parallel to each other. (6) A λ / 4 plate made of a roll-shaped polymer film,
A roll-shaped liquid crystal cell substrate in which a roll-shaped linear polarizing film is laminated, wherein the angle between the longitudinal direction of the liquid crystal cell substrate and the transmission axis of the linear polarizing film is substantially 45 °. A liquid crystal cell substrate in the form of a roll, in which the longitudinal direction of and the slow axis of the λ / 4 plate are substantially parallel.

(7) A liquid crystal display device having a liquid crystal sandwiched between two substrates, wherein the substrate on the side opposite to the display surface has a reflection means, and the substrate on the display surface side is (5). Or (6)
A reflective liquid crystal display device, which is a substrate obtained by cutting the roll-shaped liquid crystal cell substrate described in (3). (8) A liquid crystal display device comprising a liquid crystal sandwiched between two substrates, wherein the substrate on the side opposite to the display surface has a semi-transmissive means, and the substrate on the display surface side is (5) or ( A transflective liquid crystal display device, which is a substrate obtained by cutting the rolled liquid crystal cell substrate described in 6). (9) A liquid crystal display device comprising a liquid crystal sandwiched between two substrates, wherein the substrate opposite to the display surface is (5) or (6).
A semi-transmissive liquid crystal display device, which is a substrate obtained by cutting the roll-shaped liquid crystal cell substrate described in 1. (10) The transflective liquid crystal display device according to (9), wherein the substrate on the display surface side is also a substrate obtained by cutting the rolled liquid crystal cell substrate according to (5) or (6). (11) The liquid crystal display device according to any one of (1) to (10), in which liquid crystal molecules are substantially vertically aligned with no voltage applied.

In the present specification, "substantially 45
“°” or “substantially parallel” means a strict angle of ± 5
It means that the range is less than °. The angle error is ±
It is preferably less than 4 °, more preferably less than ± 3 °, even more preferably less than ± 2 °, and most preferably less than ± 1 °.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION [λ / 4 Plate] In the present invention, a λ / 4 plate is used.
A roll-shaped polymer film is used as the plate. The λ / 4 plate preferably satisfies λ / 4 in a wide wavelength range. The retardation value (Re450) of the λ / 4 plate measured at a wavelength of 450 nm is preferably 60 to 135 nm, more preferably 108 to 120 nm. The retardation value (Re590) of the λ / 4 plate measured at a wavelength of 590 nm is 100 to 170.
It is preferably nm. Also, Re590-Re4
It is preferable that the relationship of 50 ≧ 2 nm is satisfied, and Re5
90-Re450 ≧ 5 nm is more preferable, and Re590-Re450 ≧ 10 nm is most preferable.

The retardation value (Re) is calculated according to the following formula. Retardation value (Re) = (nx−ny) × d where nx is the refractive index in the plane of the retardation plate in the slow axis direction (maximum refractive index in the plane); ny is the position Is the refractive index in the direction perpendicular to the slow axis in the plane of the retarder; and d is
It is the thickness (nm) of the retardation film.

Examples of polymers constituting the λ / 4 plate are polyvinyl alcohol, polycarbonate, cellulose ester (eg, cellulose triacetate, cellulose diacetate), polyolefin, polysulfone, polyether sulfone, norbornene resin, polyester (eg, polyethylene). Terephthalate, polyethylene naphthalate), polyimide, polyamide, polyarylate, polyetherketone and polystyrene. Commercially available polymers (for example, modified copolymerized polycarbonate of Teijin Limited, Zeonoa and Zeonex of Nippon Zeon Co., Ltd., and Arton which is a norbornene resin manufactured by JSR Corporation) may be used. As the λ / 4 plate, a film (WO00 / 658) obtained by uniaxially stretching polycarbonate, cellulose ester or polyolefin is used.
It is preferable to use (No. 4 specification) as a plastic substrate as it is. A λ / 4 plate in which the slow axis is inclined substantially 45 ° with respect to the longitudinal direction can be produced by obliquely stretching the polymer film.

[Linear Polarizing Film] In the present invention, a roll-shaped linear polarizing film is used. A commercially available product can be used as the roll-shaped linear polarizing film in which the width direction and the transmission axis are substantially parallel to each other. The linearly polarizing film is a method of dissolving or adsorbing dichroic molecules such as iodine or dye, and stretching the film in one direction to arrange the dichroic molecules, and the above-mentioned dichroic molecule on a film stretched in a uniaxial direction. , A bisazo compound, a tautomer thereof, or a salt thereof, which is prepared using a dichroic dye containing a water-soluble organic dye, or a bistriazine compound, a tautomer thereof, and a salt thereof. Can be prepared by any of the methods using a water-soluble compound selected from In the application of the liquid crystal display device, heat is often generated in the formation of each element (eg, color filter, gas barrier layer, transparent electrode layer, switching element) of the liquid crystal display device. Therefore, it is preferable to use a linear polarizing film having excellent heat resistance. Further, in the application of the liquid crystal display device, a vacuum state may be formed by forming each element (eg, gas barrier layer, transparent electrode layer, switching element) of the liquid crystal display device. Therefore, it is preferable to use a linear polarizing film whose transmittance and degree of polarization do not easily change even in a vacuum state.

The linear polarizing film preferably has a high transmittance from the viewpoint of enhancing the contrast of the liquid crystal display device. The transmittance is preferably 30% or more, and more preferably 40% or more at a wavelength of 550 nm. The higher the degree of polarization of the linear polarizing film is, the more preferable. The degree of polarization is 95 at a wavelength of 550 nm.
0% or more is preferable, 99% or more is more preferable, 9
Most preferably, it is 9.9% or more.

The transmission axis is substantially 45 ° with respect to the longitudinal direction.
The tilted linearly polarizing film holds both ends of the roll-shaped polymer film by holding means and applies tension while advancing the holding means in the longitudinal direction of the film, thereby substantially holding the starting point of one end of the polymer film. To a substantial holding release point (L1), and a holding means locus from the substantial holding start point at the other end of the polymer film to the substantial holding release point (L2); The distance (W) of the specific holding release point satisfies the following formula (1), maintains the supportability of the polymer film, and is stretched in the presence of a state where the volatile content is 5% or more, and then contracted to reduce the volatile content. Can be obtained by lowering. Formula (1) | L2-L1 |> 0.4W

Explaining in more detail with reference to FIG. 1, such a method for stretching a polarizing film is such that a raw film shown in (a), for example, a polyvinyl alcohol polymer film is introduced in the direction of arrow (a). And (b) the width direction stretching step, and (c) the stretched film shown in the next step, that is, the step of feeding in the (b) direction. These (a) to (c) are hereinafter referred to as the “stretching step”.
Including the steps, it refers to the entire steps for carrying out the stretching method of the present invention. The film is continuously introduced from the direction of (a), and is first held by the holding means on the left side when viewed from the upstream side at the point B1. At this point, one film edge is not held yet and no tension is generated in the width direction. That is, B
One point does not correspond to the substantial holding start point (hereinafter, referred to as “substantial holding start point”) of the present invention.

The substantial holding start point is defined as a point where both ends of the film are held for the first time. The substantial holding start point is two points, namely, the holding start point A1 on the further downstream side and the point C1 where a straight line drawn from A1 substantially perpendicular to the center line 21 of the introduction side film intersects with the trajectory 23 of the holding means on the opposite side. Shown. Starting from this point, when the holding means at both ends is conveyed at substantially the same speed, A1 moves to A2, A3 ... An and C1 similarly moves to C2, C3 ... Cn every unit time. To do. That is, the points An and C through which the holding means serving as the reference pass at the same point
The straight line connecting n is the stretching direction at that time.

In this method, since An gradually lags behind Cn as shown in FIG. 1, the stretching direction is gradually inclined from the direction perpendicular to the conveying direction. Substantial holding release point (hereinafter,
The "substantial holding release point" is a point of Cx that departs from the holding means further upstream, and a straight line drawn substantially perpendicular to the center line 22 of the film sent from Cx to the next process is the trajectory of the holding means on the opposite side. It is defined by two points Ay intersecting 24. The angle of the final film stretching direction is the stroke difference A between the left and right holding means at the end point (substantially holding release point) of the substantial stretching process.
It is determined by the ratio of y-Az (that is, | L1-L2 |) and the distance W (the distance between Cx and Ay) of the substantial holding release point. Therefore, the inclination angle θ formed by the stretching direction with respect to the conveyance direction to the next step is tan θ = W / (Ay−Ax), that is, an angle satisfying tan θ = W / | L1-L2 |. The upper film edge in FIG. 1 is Ay.
Even after the point, up to 28 is held, but since the other end is not held, new width-direction stretching does not occur, and 28 is not substantially the holding release point.

As described above, the substantial holding start points at both ends of the film are not the simple biting points into the left and right holding means. The two substantial holding start points are, if the above definition is described more strictly, a straight line connecting either the left or right holding point and the other holding point is the center line of the film introduced into the step of holding the film. Is almost orthogonal to
And these two holding points are defined as being located at the most upstream. Similarly, the two substantial holding release points are points at which the straight line connecting either the left or right holding point and the other holding point is substantially orthogonal to the center line of the film sent to the next process, and These two holding points are defined as being the most downstream. Here, “substantially orthogonal” means that the straight line connecting the center line of the film and the left and right substantial holding starting points or substantial holding releasing points is 90 ± 0.5 °.

When an attempt is made to make a difference between the left and right strokes by using a tenter type drawing machine, a large deviation often occurs between the biting point into the holding means and the actual holding start point due to mechanical restrictions such as rail length. A large deviation may occur between the detachment point from the holding means and the substantial holding release point, but the process between the substantial holding start point and the substantial holding release point defined above may satisfy the relationship of the formula (1). .

In the above, the inclination angle of the orientation axis in the obtained stretched film is controlled and adjusted by the ratio of the exit width W of the step (c) and the stroke difference | L1-L2 | of the two left and right substantial holding means. be able to. 45 in the longitudinal direction
In order to obtain an orientation angle close to °, it is more preferable to satisfy the following formula (2), and it is more preferable to satisfy the following formula (3). Formula (2) 0.9W <| L2-L1 | <1.1W Formula (3) 0.97W <| L2-L1 | <1.03W

The film introduction direction (a) into the stretching step,
The angle formed by the film transport direction (b) to the next process can be any value, but from the viewpoint of minimizing the total installation area of the equipment including the process before and after stretching, the smaller angle is It is preferably within 3 °, more preferably within 0.5 °. Stretching while applying tension while holding both ends of the continuously supplied polymer film by holding means is preferably 1.1 to 20.0 times, and 1.1 to 10. Stretching to 0 times is more preferable, and stretching to 2 to 10 times is most preferable. The contraction rate after stretching is preferably 10% or more.

Further, from the viewpoint of minimizing the equipment cost of the stretching step, the smaller the number of times of bending of the locus of the holding means and the bending angle, the better. From this point of view, as illustrated in FIG. 1, the angle between the film advancing direction at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is 20 to 20.
It is preferable to bend the film so that the film advancing direction is inclined at 70 ° while holding both ends of the film. In the case of a tenter type stretching machine, there are many structures in which a chain to which a clip is fixed advances along a rail. However, when a left-right uneven stretching method is adopted as in the present invention, as shown in FIG. 1 as a result. The rail ends may shift at the process entrance and exit, and the rails may be bitten at the same time and not disengage. in this case,
The substantial process lengths L1 and L2 are not the simple biting-disengaging distances as described above, but are the stroke lengths of the portions where the holding means holds both ends of the film, as already mentioned. .

If there is a difference in the advancing speed on the left and right of the film at the exit of the drawing process, wrinkles and deviations occur at the exit of the drawing process. Therefore, the conveying speed of the left and right film gripping means is required to be substantially constant. To be The speed difference between left and right is 3
% Or less is preferable, less than 1% is more preferable, and 0.0
Most preferred is less than 5%. The transport speed of the film gripping means is the length of the trajectory of the left and right holding means per minute. In a typical tenter stretching machine, etc., there is speed unevenness that occurs on the order of seconds or less depending on the cycle of the sprocket teeth that drive the chain, the frequency of the drive motor, etc. It does not correspond to the speed difference.

Further, as the difference between the left and right strokes is generated, the film is wrinkled, deviated, and the stretching axis is varied. In order to solve this problem, the polymer film is supported, the volatile content is stretched in the state where the volatile content is 10% or more, and then the film is contracted to reduce the volatile content. The volatile content represents the volume of volatile components contained in a unit area of the film, and is a value obtained by dividing the volatile component volume by the film volume. As a method of containing a volatile component, a film may be cast to contain a solvent or water, dipping / coating / spraying in a solvent or water before stretching, or coating a solvent or water during stretching. Since the polyvinyl alcohol film contains water in a high-temperature and high-humidity atmosphere, it can contain a volatile component by stretching after conditioning in a high-humidity atmosphere or under high-humidity conditions. Other than these methods, the volatile content of the polymer film can be increased to 10% or more. In the case of polyvinyl alcohol film, the preferable volatile content is 10 to 100%.

The shrinkage of the stretched polymer film is
It may be performed in any step after stretching. It is sufficient that the shrinkage eliminates the wrinkles of the polymer film and the variation in the stretching axis that occur when the film is oriented in an oblique direction. As a means for shrinking the film, a method of removing volatile matter by heating can be adopted. The shrinkage rate of the film is preferably 1 / sin θ times or more, where θ is the orientation angle with respect to the longitudinal direction. The value of shrinkage is preferably 10% or more.

The wrinkles of the polymer film generated when the film is oriented in an oblique direction need only disappear by the point where the retention is substantially released. However, if it takes time from the generation of wrinkles to their disappearance, variations in the stretching direction may occur. It is preferable that the wrinkles disappear from the point where the wrinkles occur at a transition distance as short as possible. For that purpose, a method of increasing the volatilization rate of the volatile content is effective.

When a long-sized, particularly roll-shaped polarizing film is produced in an integrated process, it is necessary that there be no uneven dyeing or omission. If there is uneven distribution of the volatile components in the film before stretching (difference in the amount of volatile components depending on the location within the film surface), uneven dyeing and loss may occur. Therefore, the content distribution of the volatile component in the film before stretching is preferably small, and is preferably at least 5% or less. The volatile content is a value obtained by dividing the volume of the volatile component contained in a unit volume of the film with a Japanese paper and dividing the volatile component volume by the film volume. The distribution of the volatile component represents a fluctuation range of the volatile content per 1 m ² (ratio of the larger difference between the maximum value or the minimum value and the average volatile content to the average volatile content). As a method of reducing the content distribution of the volatile component, a method of blowing the front and back surfaces of the film with uniform air, uniformly squeezing with a nip roller, or wiping with a wiper can be adopted.

[Circular Polarizing Plate] The circular polarizing plate is a roll-shaped λ /
It can be manufactured by laminating the four plates and the roll-shaped linear polarizing film by roll-to-roll.

[Liquid Crystal Cell Substrate] The circularly polarizing plate has various uses, and the circularly polarizing plate according to the present invention can be particularly advantageously used as a liquid crystal cell substrate. The liquid crystal cell substrate holds a liquid crystal having fluidity and plays an important role in maintaining the shape of the liquid crystal cell. The liquid crystal cell substrate is required to have a high transmittance for visible light, be stable thermally and mechanically, have flexibility, and have strength for supporting a liquid crystal display device. The circularly polarizing plate according to the present invention can be used as it is as a plastic substrate of a liquid crystal cell. In this case, the λ / 4 plate functions as the substrate. The plastic substrate has, in addition to the function as a circularly polarizing plate, a gas barrier layer, a transparent electrode, an antireflection or antiglare layer, a color filter layer, a semitransparent film layer, a reflective electrode having an opening, a switching element (eg, TFT, TF
D) may be included.

A gas barrier layer, a transparent electrode, a color filter layer, a semi-transmissive film layer, on a λ / 4 plate constituting a circularly polarizing plate,
A reflective electrode having an opening, a switching element (eg, TF
T, TFD) can be formed. Also, a gas barrier layer, a transparent electrode, a color filter layer, a semi-transmissive film layer, a reflective electrode having an opening, a switching element (eg, TFT, TFD).
Another polymer film formed with may be laminated with the circularly polarizing plate. Examples of polymers used for other polymer films include polyvinyl alcohol resins, polycarbonate derivatives (Teijin Limited: modified, copolymerized polycarbonate), cellulose derivatives (cellulose triacetate, cellulose diacetate), polyolefin resins (Nippon ZEON ( Co., Ltd .: Zeonoa, Zeonex), polysulfone resin, polyether sulfone, norbornene resin (JSR Corporation: Arton), polyester resin (PET, PEN), polyimide resin, polyamide resin, polyarylate resin , Polyetherketone is included. Polycarbonate derivative, cellulose derivative,
Polyolefin resins and norbornene resins are preferable, and polycarbonate derivatives are particularly preferable.

In the present invention, a plastic substrate may be used for either the display surface side or the display surface opposite side, and it is preferable to use the plastic substrate for both the substrates in order to reduce the thickness and weight.

[Transparent Electrode] The transparent electrode provided on the plastic substrate preferably has a surface resistivity of 10 ³ Ω / □ or less, and more preferably 100 Ω / □ or less. In order to obtain the surface resistivity of the transparent electrode as described above, a method of applying a conductive fine particle dispersion, a metal alkoxide or the like, a vacuum film forming method such as sputtering, vacuum deposition method, ion plating method or CVD method. Or a vapor phase growth method under atmospheric pressure is preferable.

As the material of the transparent electrode, metal oxides such as In ₂ O ₃ system (including doped products such as Sn), SnO ₂ system (including doped products such as F and Sb), ZnO system (Al, Ga) are used.
Such as doped products), TiO ₂ , Al ₂ O ₃ , SiO ₂ ,
Examples thereof include MgO, BaO, MoO ₃ , V ₂ O ₅ , or a composite product of these, such as In ₂ O ₃ —ZnO system. Furthermore, examples of the metal nitride include TiN.

As a method for forming a film containing mainly indium oxide by a sputtering method, reactive sputtering using a metal target containing indium as a main component or a target which is a sintered body containing indium oxide as a main component is carried out. It can be carried out. The latter is preferable in terms of controlling the reaction. In the reactive sputtering method, an inert gas such as argon is used as the sputtering gas, and oxygen is used as the reactive gas. DC as the discharge type
Magnetron sputtering, RF magnetron sputtering, etc. can be used. Further, as a method for controlling the flow rate of oxygen, it is preferable to use a plasma emission monitor method.

[Gas Barrier Layer] The gas barrier layer prevents water, organic substances, air, etc. from the plastic substrate or the color filter from changing the state of the liquid crystal and deteriorating the durability of the liquid crystal display device. Therefore,
The gas barrier layer is preferably made of a material having low permeability such as water, organic matter and air, for example, an inorganic oxide such as silicon oxide, a metal, a nonmetal, or an oxide of a submetal. The gas barrier layer is preferably located between the λ / 4 plate and the transparent electrode or between the color filter and the transparent electrode.

Silicon oxide is an oxide of Si such as SiO and SiO ₂ , and is expressed as SiOx. Gas barrier properties,
From the viewpoint of transparency, surface smoothness, flexibility, etc., a metal oxide containing a silicon oxide as a main component in which the ratio of the number of oxygen atoms to the number of silicon atoms is 1.5 to 2.0 is preferable. The ratio of the number of oxygen atoms to the silicon oxide is analyzed and determined by X-ray electron spectroscopy, X-ray micro-spectroscopy, Auger electron spectroscopy, Rutherford backscattering, etc. If this ratio is less than 1.5, the transparency will deteriorate, so 1.5 to 2.0
Is preferred.

Specific preferred examples of the gas barrier layer include aluminum oxide, zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, chromium oxide, silicon oxide and cobalt oxide.
Zirconium oxide, tin oxide, titanium oxide, iron oxide, copper oxide, nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesium oxide, manganese oxide, molybdenum oxide, vanadium oxide, barium oxide and the like, but silicon oxide. Aluminum oxide is particularly preferable because it has high oxygen barrier properties, water vapor barrier properties, and transparency, and is industrially inexpensive.

The silicon oxide and aluminum oxide may be used alone or as a mixture. The metal oxide may contain trace amounts of metals, non-metals, simple sub-metals or hydroxides thereof, or carbon, fluorine or magnesium fluoride as appropriate for improving plasticity.

The thickness of the metal oxide layer is 5 to 20.
The range of 0 nm is preferred. If the thickness is less than 5 nm, it is difficult to form a film uniformly, and a part where the film is not formed is generated, and gas may permeate from this part to deteriorate the gas barrier property. On the other hand, when the thickness is more than 200 nm, not only the transparency is deteriorated but also cracks are likely to occur, which may impair the gas barrier property.

The sputtering method is mainly used for forming the metal oxide layer. For example, in a sputtering method for forming a layer containing silicon oxide SiOx, a sintered body containing silicon or silicon oxide as a main component can be used as a target. The former introduces an inert gas such as argon and a reactive gas such as oxygen gas into a vacuum chamber to perform reactive sputtering. In the latter, sputtering is performed using a mixture of an inert gas such as argon and a reactive gas such as a small amount of oxygen gas. As the sputtering method, known methods such as direct current or high frequency bipolar sputtering, direct current or high frequency magnetron sputtering, and ion beam sputtering can be applied. Among them, the magnetron method is preferable because it has less plasma impact on the substrate and enables high-speed film formation. In the present invention, it is particularly preferable to perform film formation by DC magnetron sputtering using a Si metal target in order to increase the film formation rate. Although a Si oxide target may be used in some cases, it is not preferable from the viewpoint of productivity because the film forming rate is extremely slow and the discharge stability is poor. Further, as the sputtering apparatus, a roll-to-roll method is desirable from the viewpoint of productivity, but a batch method can also be used.

[Color Filter] The color filter is preferably produced by a dye method, a pigment dispersion method, a printing method, an electrodeposition method, a spin coating method or the like. A transfer method using a photosensitive transfer material described in JP-A-5-80503, a photographic method using a silver halide color light-sensitive material described in JP-A-7-294714, and a JP-A-7-29.
It is particularly preferable to manufacture by a laser method using the image forming system described in Japanese Patent Publication No. 0731.

The color filter may be installed between the λ / 4 plate and the gas barrier layer, or may be installed in the order of the λ / 4 plate, the gas barrier layer and the color filter. The color filter of the present invention is preferably installed on the plastic substrate on the display side or on the drive circuit on the opposite side.

[Antireflection Layer / Antiglare Layer] The antireflection layer / antiglare layer is preferably an antireflection layer formed of a thin interference layer. Further, as the antiglare layer, a scattering layer having irregularities on the surface or particles having different refractive indexes inside is preferable.

Japanese Examined Patent Publication No. 60-59250 discloses an antireflection layer having fine pores and inorganic fine particles. JP-A-59-50401 discloses an antireflection film in which a support, a high refractive index layer and a low refractive index layer are laminated in this order. The publication also discloses an antireflection film in which a medium refractive index layer is provided between a support and a high refractive index layer. The low refractive index layer is formed by coating a polymer or inorganic fine particles. Japanese Unexamined Patent Publication No. 2-245702 discloses an antireflection film in which two or more kinds of ultrafine particles (for example, MgF ₂ and SiO ₂ ) are mixed and the mixing ratio is changed in the film thickness direction. The refractive index is changed by changing the mixing ratio to obtain the same optical properties as the antireflection film having the high refractive index layer and the low refractive index layer described in JP-A-59-50401. ing. The ultrafine particles are adhered by SiO2 produced by thermal decomposition of ethyl silicate. In the thermal decomposition of ethyl silicate, carbon dioxide and water vapor are also generated by the combustion of ethyl part. JP-A-2-245
As shown in FIG. 1 of Japanese Patent Laid-Open No. 702, a gap is generated between the ultrafine particles due to the separation of carbon dioxide and water vapor from the layer.

Japanese Unexamined Patent Publication (Kokai) No. 5-13021 discloses filling the gap between the ultrafine particles present in the antireflection film described in Japanese Unexamined Patent Publication (Kokai) No. 2-245702 with a binder. Japanese Unexamined Patent Publication No. 7-48527 discloses an antireflection film containing an inorganic fine powder made of porous silica and a binder. Further, JP-A-2001-100004 discloses that at least one layer has a refractive index of 1.38 or more and 1.4 or more.
An antiglare antireflection film provided with a low refractive index layer containing a fluorine-containing resin of 9 or less, comprising a binder having a refractive index of 1.57 to 2.00 between a base material and the low refractive index layer. A method for forming an antiglare antireflection film provided with an antiglare layer is disclosed. The antireflection / antiglare layer may be formed by sequentially providing the antiglare layer and the low refractive index layer on the substrate. It is preferable to further provide the above-mentioned hard coat layer, and two or more hard coat layers having different constituents may be provided. The antireflection / antiglare layer is formed on the outermost surface of the plastic substrate. preferable.

[Reflective Liquid Crystal Display] The mode of the liquid crystal display is not particularly limited, but TN (twisted nematic)
Type, VA (Vertical Alingment) type, HAN (Hybrid A)
liged Nematic) type, STN (Supper Twisted Nemati)
c) type or GH (Guest Host) type is preferable.

The twist angle of the TN type liquid crystal cell is preferably 40 to 100 °, more preferably 50 to 90 °, and most preferably 60 to 80 °. The value (Δnd) of the refractive index anisotropy (Δn) of the liquid crystal layer and the thickness (d) of the liquid crystal layer is 0.1 to 0.5.
The thickness is preferably μm, more preferably 0.2 to 0.4 μm. The TN type liquid crystal cell can be used in a simple matrix system without a drive circuit and an active matrix system with a drive circuit. An active matrix system having a driving circuit is more preferable.

The twist angle of the STN type liquid crystal cell is 180.
It is preferably from 360 to 360 °, and 220 to 270
More preferably, The value (Δnd) of the refractive index anisotropy (Δn) of the liquid crystal layer and the thickness (d) of the liquid crystal layer is preferably 0.3 to 1.2 μm,
More preferably, it is 5 to 1.0 μm. STN
Type liquid crystal cell is a simple matrix system without a drive circuit,
And it can be used in an active matrix system with a drive circuit.

In the HAN type liquid crystal cell, it is preferable that the liquid crystal is substantially vertically aligned on one substrate and the pretilt angle on the other substrate is 0 to 45 °. The value (Δnd) of the refractive index anisotropy (Δn) of the liquid crystal layer and the thickness (d) of the liquid crystal layer is preferably 0.1 to 1.0 μm, and 0.3 to 0.8 μm. It is more preferable that there is. The substrate on the side of vertically aligning the liquid crystal may be the substrate on the reflection plate side or the substrate on the transparent electrode side.

In the GH type liquid crystal cell, the liquid crystal layer is composed of a mixture of liquid crystal and dichroic dye. When both the liquid crystal and the dichroic dye are rod-shaped compounds, the director of the liquid crystal and the long axis direction of the dichroic dye are parallel to each other. When the alignment state of the liquid crystal changes due to the application of a voltage, the dichroic dye also changes in the major axis direction like the liquid crystal. GH type liquid crystal cells include Heilmeer type,
White-Taylor using cholesteric liquid crystal
Although a mold, a two-layer type, a method using a λ / 4 plate, etc. are known, it is preferable to use a method using a λ / 4 plate in the present invention. Regarding the guest-host reflection type liquid crystal display device provided with a λ / 4 plate, JP-A-6-222350, 8-36174, 10-268300 and 10-
292175, 10-293301, 10-3
No. 11976, No. 10-319442, No. 10-32.
5953, 10-333138, 11-384.
It is described in each publication of No. 10. The λ / 4 plate is provided between the liquid crystal layer and the reflection plate. The liquid crystal layer may use either horizontal alignment or vertical alignment, but it is preferable to use vertical alignment. The dielectric constant anisotropy of the liquid crystal is preferably negative.

In the VA type liquid crystal cell, the liquid crystal is vertically aligned between the two substrates when no voltage is applied. Generally, a liquid crystal having a negative dielectric anisotropy is used, and the liquid crystal is horizontally aligned by applying a voltage between the upper and lower electrodes. Generally used in normally black mode, it provides a very high contrast ratio. Negative uniaxial or negative biaxial retardation films are combined to improve the viewing angle dependence. Further, it is disclosed in JP-A No. 11-258605 that the viewing angle dependency can be improved by providing a projection or a depression on the electrode or by using a slit-shaped electrode. The value (Δnd) of the refractive index anisotropy (Δn) of the liquid crystal layer and the thickness (d) of the liquid crystal layer is 0.1 to 1.0 μm.
Is preferable, and 0.3 to 0.6 μm is more preferable. A method of horizontally aligning the liquid crystal by applying an electric field in the horizontal direction of the substrate to the liquid crystal having positive dielectric anisotropy can also be considered as one of the VA type liquid crystal cells.

The reflective liquid crystal display device is used in a normally white mode in which bright display is performed when the applied voltage is low and dark display when the applied voltage is high, and in a normally black mode in which dark display is applied when the applied voltage is low and bright display is applied when the applied voltage is high. be able to.

As a driving method of the reflective or semi-transmissive liquid crystal display device, an active matrix method is preferable to a simple matrix method, and a TFT (Thin Film) is used.
Transistor), TFD (Thin Film Diode) or MI
It is more preferable to use M (Metal Insurator Metal). More preferably, low temperature polysilicon or continuous grain boundary silicon is used for the TFT.

For details, see “Liquid Crystal Device Handbook” edited by Japan Society for the Promotion of Science, 142nd Committee, Nikkan Kogyo Shimbun, “Liquid Crystal Applied” by Mitsuharu Okano et al., Baifukan, “Color Liquid Crystal Display” by Shunsuke Kobayashi et al. "Next-generation liquid crystal display technology" Tatsuo Uchida, Industrial Research Committee, "Cutting-edge of liquid crystal display" edited by Young Researchers of Liquid Crystal, Sigma Publishing,
"Liquid crystal: LCD basics and new applications" It is described in Liquid Crystal Young Research Group, Sigma Publishing, etc.

[0056]

[Example 1] (Preparation of linearly polarizing film) PVA film having an average degree of polymerization of 4000 and a degree of saponification of 99.8% mol was treated with 1.0 g of iodine /
1, dipped in an aqueous solution of potassium iodide 60.0 g / l at 25 ° C. for 30 seconds, further dipped in an aqueous solution of boric acid 40 g / l and potassium iodide 30 g / l at 25 ° C. for 120 seconds,
Introduced into a tenter stretching machine for stretching in a direction in which the transmission axis is inclined 45 ° with respect to the longitudinal direction, and stretched twice in an atmosphere of 60 ° C and 90%, and the tenter is repeatedly bent and contracted in the stretching direction. After being dried in an atmosphere of 80 ° C., it was separated from the tenter. The water content of the PVA film before the stretching is 3
The water content was 1% and the water content after drying was 1.5%. The difference in conveyance speed between the left and right tenter clips was less than 0.05%, and the angle formed by the center line of the film introduced and the center line of the film sent to the next step was 0 °. Where | L
1-L2 | is 0.7 m, W is 0.7 m, and | L1-
There was a relationship of L2 | = W. The substantial stretching direction at the exit of the tenter was inclined by 45 ° with respect to the center line of the film sent to the next step. No wrinkles or film deformation was observed at the tenter exit. In this way, a roll-shaped linear polarizing film POL-1 having a length of 1000 m with the absorption axis inclined at 45 ° in the longitudinal direction was produced. Obtained linear polarizing film P
The width of OL-1 was 650 mm and the thickness was 20 μm.

(Preparation of λ / 4 Plate) Bisphenol A and biscresol fluorene were dissolved in a sodium hydroxide aqueous solution and ion-exchanged water at a molar ratio of 1: 2, and a small amount of hydrosulfite was added. Next, methylene chloride was added, and phosgene was blown in at 20 ° C. for 65 minutes. Further, p-tert-butylphenol was added to emulsify, triethylamine was added, and the mixture was stirred at 30 ° C. for about 3 hours to terminate the reaction. After completion of the reaction, the organic phase was separated and methylene chloride was evaporated to obtain a polycarbonate copolymer. A polycarbonate copolymer was dissolved in methylene chloride, and a roll-shaped cast film was produced from this dope solution. Roll-shaped λ / 4 plate QF with a length of 1000 m that is uniaxially longitudinally stretched 1.7 times at a temperature of 215 ° C.
-1 film was obtained. The obtained λ / 4 plate QF-1 had a thickness of 90 μm and a width of 680 mm, and the ellipsometer (K
OBRA-31PR, manufactured by Oji Scientific Instruments Co., Ltd.
Wavelength 450nm, 550nm, 590nm, 700nm
Of the retardation value (Re) in 118.5 nm, 150.0 nm and 15
It was 4.1 nm and 158.9 nm. The slow axis was parallel to the longitudinal direction of the roll film.

(Production of Plastic Substrate on Display Side) A coating solution having the following formulation H1 was applied onto a polyethylene terephthalate film temporary support having a thickness of 100 μm and dried to form a thermoplastic resin layer having a dry film thickness of 20 μm. Was set up. Thermoplastic resin layer formulation H1: Methyl methacrylate / 2-
Ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 5
5 / 28.8 / 11.7 / 4.5, weight average molecular weight = 9
0000) 15 parts by weight, polypropylene glycol diacrylate (average molecular weight = 822) 6.5 parts by weight, tetreethylene glycol dimethacrylate 1.5 parts by weight
p-toluenesulfonamide, 0.5 parts by weight benzophenone 1.0 parts by weight, methyl ethyl ketone 30 parts by weight Next, a coating solution having the following formulation B1 was applied onto the thermoplastic resin layer and dried to give a dry film thickness of 1. A 6 μm intermediate layer was provided. Intermediate layer formulation B1: Polyvinyl alcohol (Kuraray Co., Ltd.)
PVA205, saponification rate = 80%, 130 parts by weight, polyvinylpyrrolidone (PV manufactured by GAF Corporation)
P, K-90) 60 parts by weight, fluorine-based surfactant (Surflon S-131 manufactured by Asahi Glass Co., Ltd.) 10 parts by weight Distilled water
3350 parts by weight On the four temporary supports having the thermoplastic resin layer and the intermediate layer, black (for Bl layer), red (for R layer), green (G
Layer) and blue (for layer B) four color photosensitive solutions are applied,
It was dried to form a colored photosensitive resin layer having a dry film thickness of 2 μm. Further, polypropylene (a cover sheet having a thickness of 12 μm was pressure-bonded onto the photosensitive resin layer to prepare red, blue, green and black photosensitive transfer materials.

Using this photosensitive transfer material, a color filter was prepared by the following method. The cover sheet of red photosensitive transfer material is peeled off, and the width of the photosensitive resin layer surface is 680 mm.
On a roll film λ / 4 plate QF-1 of No. 2 using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.) by pressing (0.8 kg / cm ² ), heating (120 ° C.), and then bonding. Then, the temporary support was peeled off at the interface between the temporary support and the thermoplastic resin layer to remove the temporary support. Next, it was exposed to light through a predetermined photomask to remove the thermoplastic resin layer and the intermediate layer with a 1% triethanolamine aqueous solution. At this time, the photosensitive resin layer was not substantially developed. Then, the photosensitive resin layer was developed with a 1% sodium carbonate aqueous solution to remove unnecessary portions, and a red pixel pattern was formed on the λ / 4 plate. Then, a green photosensitive transfer material was attached and peeled off on the λ / 4 plate on which the red pixel pattern was formed in the same manner as above.
Exposure and development were performed to form a green pixel pattern. Repeat the same process with blue and black photosensitive transfer materials,
Color filters were formed on the four plates. In these steps, the temporary support showed satisfactory releasability from the thermoplastic resin layer, and the obtained color filter had no missing pixels, good adhesion to the base, and no stain.

Further, the roll film-shaped λ / 4 plate on which this color filter is formed is set in a winding type sputtering device, and a thickness of 10 nm is formed on the color filter.
SiOx gas barrier layer of 150 n
m In ₂ O ₃ based transparent electrode was formed. The surface resistivity of the transparent electrode was measured by the four-terminal method described in JIS H 0602: 1995, and the result was 15Ω / □. The oxygen permeability of this plastic substrate was measured by a different pressure method and found to be 1.0 cc / square meter · 24 hours · atmosphere or less.

A vertical alignment film (SE-1211, manufactured by Nissan Chemical Industries, Ltd.) on a roll film plastic substrate having a color filter layer, a gas barrier layer and a transparent electrode layer formed thereon.
Product) was continuously applied and heat-treated to form a color filter layer, a gas barrier layer, a transparent electrode layer, and an alignment film λ /
Four plates were produced.

(Formation of Antireflection Layer / Antiglare Layer) The antireflection layer / antiglare layer on the protective film of the polarizing plate is described in JP-A-2001-2001.
In the same manner as described in JP-A No. 100004 and Example 1, triacetyl cellulose film (trade name: TAC-TD8
0U, manufactured by Fuji Photo Film Co., Ltd., was coated with a coating solution A for an antiglare layer using a bar coater, dried at 120 ° C., and then a 160 W / cm air-cooled metal halide lamp (I Graphics Co., Ltd.). Illuminance 400 mW /
cm ^2, and an irradiation dose of 300 mJ / cm ² to cure the coating layer, to form an antiglare layer having a thickness of about 1.5 [mu] m. A low-refractive-index layer coating solution is applied thereon using a bar coater, dried at 80 ° C., and then at 120 ° C. for 10 hours.
Thermal crosslinking was carried out for a minute to form a low refractive index layer having a thickness of 0.096 μm.

Polyvinyl alcohol adhesive is applied to both sides of the linear polarizing film POL-1 having a transmission axis of 45 ° with respect to the longitudinal direction, and the polycarbonate side of the λ / 4 plate is applied to one side. The cellulose triacetate film (protective film) to which the above antireflection layer / antiglare layer had been previously provided on the opposite side was laminated with the antireflection layer / antiglare layer side by roll-to-roll. Further dried at 80 ° C., it has a function as a circularly polarizing plate having a width of 680 mm, and has a color filter, a gas barrier layer, a transparent electrode, an alignment film, an antireflection layer / antiglare layer, and a thickness of 0.2 mm. A plastic substrate SUB-1 on the display surface side was obtained. The effective width of this plastic substrate is 650mm, so it is 42 "max.
It can handle panel sizes up to (aspect ratio = 4: 3).

(Production of Reflection Type Liquid Crystal Display Device) 550 mm × 650 m in which 4 sets of 1 set of TFT array consisting of reflection electrodes and driving polysilicon of 13.3 inches are formed.
A glass substrate opposite to m was prepared. A vertical alignment film (SE-1211, manufactured by Nissan Chemical Industries, Ltd.) was applied to the electrode side of this glass substrate, and the coating was further performed at 80 ° C. for 15 minutes for 180 minutes.
A heat treatment was performed at 60 ° C. for 60 minutes, and a rubbing treatment was performed in the short side direction of the glass substrate. The roll film plastic substrate SUB-1 was cut into a sheet of 550 mm × 650 mm, and a rubbing treatment was performed in parallel with the 550 mm side of the plastic substrate SUB-1. The plastic substrate SUB-1 was superposed on the opposite substrate so that the alignment films face each other through a spacer having a particle diameter of 4 μm. At this time, the rubbing directions of the upper and lower substrates facing each other were anti-parallel. A liquid crystal having a negative dielectric anisotropy (MLC-6608,
(Manufactured by Merck & Co., Inc.) was injected to form a liquid crystal layer. In this way, a 550 mm × 650 mm VA type liquid crystal cell was produced. The obtained liquid crystal cell was cut to obtain a reflection type liquid crystal display device having four sets of 13.3 inch panels.

Example 2 (Preparation of Linear Polarizing Film) PVA film having an average degree of polymerization of 4000 and a degree of saponification of 99.8% mol was added with 1.0 g of iodine /
1, dipped in an aqueous solution of potassium iodide 60.0 g / l at 25 ° C. for 30 seconds, further dipped in an aqueous solution of boric acid 40 g / l and potassium iodide 30 g / l at 25 ° C. for 120 seconds,
The film was introduced into a longitudinal stretching machine, stretched 5 times in an atmosphere of 60 ° C and 90%, and dried in an atmosphere of 80 ° C. The obtained length 1000
The transmission axis of the roll-shaped linear polarizing film POL-2 of m was perpendicular to the longitudinal direction of the roll film, the width was 650 mm, and the thickness was 20 μm.

(Production of λ / 4 Plate) The polycarbonate copolymer synthesized in Example 1 was dissolved in methylene chloride, and a roll cast film was produced from this dope solution. The film is introduced into a tenter stretching machine for stretching in a direction in which the slow axis is inclined by 45 ° with respect to the longitudinal direction,
After stretching twice, the tenter was repeatedly bent and contracted in the stretching direction, and then released from the tenter. The difference in conveyance speed between the left and right tenter clips was less than 0.05%, and the angle formed by the center line of the film introduced and the center line of the film sent to the next step was 0 °. Here, | L1-L2 | was 0.7 m, W was 0.7 m, and there was a relationship of | L1-L2 | = W. The substantial stretching direction at the tenter outlet is
It was inclined by 45 ° with respect to the center line of the film sent to the next step. No wrinkles or film deformation was observed at the tenter exit. In this way, the roll-shaped λ / 4 having a length of 1000 m, which has been stretched and has a slow axis inclined by 45 ° in the longitudinal direction.
Board QF-2 was prepared. The obtained λ / 4 plate QF-2 has a thickness of 90 μm and a width of 680 mm, and using an ellipsometer (KOBRA-31PR, manufactured by Oji Scientific Instruments), wavelengths 450 nm, 550 nm, 590 nm, 700.
When the retardation value (Re) in nm was measured, they were 118.5 nm, 150.0 nm, and 1 respectively.
It was 54.1 nm and 158.9 nm. The slow axis was 45 ° with the longitudinal direction of the roll film.

(Production of λ / 4 plate for display surface side) Further, this roll film-shaped λ / 4 plate QF-2 was set in a winding type sputtering apparatus, and SiOx having a thickness of 10 nm was set.
Of the gas barrier layer of In ₂ of 150 nm
An O ₃ -based transparent electrode was formed. The surface resistivity of the transparent electrode was measured by the four-terminal method described in JIS-H-0602: 1995, and it was 15Ω / □. The oxygen permeability of this plastic substrate was measured by a different pressure method.
It was 0 cc / square m · 24 hours · atmospheric pressure or less.

On the transparent electrode layer formed on the above-mentioned plastic substrate, a zigzag slit-like portion having no transparent electrode was formed by a photoresist for controlling the orientation. The slits were formed so that their directions were 45 ° with respect to the longitudinal direction of the plastic substrate.

A vertical alignment film (SE is formed on a roll film plastic substrate on which a gas barrier layer and a transparent electrode layer are formed.
-1211, continuously applied by Nissan Chemical Industries, Ltd.
Heat treatment was performed to prepare a λ / 4 plate on which a color filter layer, a gas barrier layer, a transparent electrode layer, and an alignment film were formed.

Polyvinyl alcohol adhesive is applied to both sides of the linear polarizing film POL-2 whose transmission axis is perpendicular to the longitudinal direction, and the polycarbonate side of the λ / 4 plate is applied to one side of the linear polarizing film POL-2. An antireflection layer / antiglare layer-free side of a cellulose triacetate film (protective film) to which an antireflection layer / antiglare layer was previously provided on the opposite side was laminated in a roll-to-roll manner. 80 more
0.2 mm thick display surface side, which has a function as a circularly polarizing plate having a width of 680 mm and has a color filter, a gas barrier layer, a transparent electrode, an alignment film, and an antireflection layer / antiglare layer when dried at ℃ To obtain a plastic substrate SUB-2U. Since the effective width of this plastic substrate is 650 mm, a maximum panel size of 42 "(aspect ratio = 4: 3) can be supported.

(Preparation of λ / 4 Plate for Opposite Side) Roll film λ / 4 plate QF-2 was set in a winding type sputtering apparatus to form a transparent electrode layer and the like on the display side plastic substrate. 12nm thickness on the side opposite to
Of Ag semi-permeable membrane layer (transmittance 30%), thickness 1 on it
A 0 nm SiOx gas barrier layer was formed. Further, four sets of 13.3 inch TFT arrays made of polysilicon were formed thereon. Further, a color filter layer was formed on the TFT array by the transfer method as in Example 1.

The roll film-shaped λ / 4 plate was set again in the winding type sputtering device to give a thickness of 10 n.
m SiOx gas barrier layer and 150
nm In ₂ O ₃ based transparent electrode was formed. The surface resistivity of the transparent electrode was measured by the four-terminal method described in JIS H 0602: 1995, and the result was 15Ω / □. The oxygen permeability of this plastic substrate was measured by a different pressure method and found to be 1.0 cc / square meter · 24 hours · atmosphere or less. On the transparent electrode layer formed on the plastic substrate,
In order to control the orientation, a zigzag slit-like portion having no transparent electrode was formed by a photoresist. The slits were formed so that their directions were 45 ° with respect to the longitudinal direction of the plastic substrate. Moreover, the position of the slit of the transparent electrode on the opposite plastic substrate was arranged so as to be the center between the slits of the transparent electrodes on the display plastic substrate when it was overlapped with the display plastic substrate.

A vertical alignment film (SE-1211, SE-1211,
Nissan Chemical Industries Co., Ltd. is continuously applied and heat treated,
A λ / 4 plate on which a semi-transmissive film, a gas barrier layer, a TFT, a color filter layer, a transparent electrode layer and an alignment film were formed was produced.

Polyvinyl alcohol adhesive is applied to both sides of the linear polarizing film POL-2 whose transmission axis is perpendicular to the longitudinal direction, and the polycarbonate side of the λ / 4 plate is applied to one side of the linear polarizing film POL-2. A cellulose triacetate film (protective film) was laminated by roll-to-roll. Further dried at 80 ° C., it has a function as a circularly polarizing plate having a width of 680 mm, and has a semi-transmissive film, a gas barrier layer, a TFT, a color filter layer, a transparent electrode layer, an alignment film, and a thickness of 0.2.
A plastic substrate SUB-2U on the opposite side of mm was obtained. Since the effective width of this plastic substrate is 650 mm, a maximum panel size of 42 "(aspect ratio = 4: 3) can be supported.

(Production of Semi-Transmissive Liquid Crystal Display Device) Display-Plastic Plastic Substrate SUB-2U Produced as Above
And the opposite side plastic substrate SUB-2L was cut into a size of 550 mm × 650 mm. Two plastic substrates SUB-2U and SUB-2L are stacked with a spacer having a particle size of 4 μm so that the alignment films face each other, and a liquid crystal having a negative dielectric anisotropy (MLC-6608, (Manufactured by Merck & Co., Inc.) was injected to form a liquid crystal layer. In this way, a 550 mm × 650 mm VA type liquid crystal cell was produced. The obtained liquid crystal cell was cut to obtain a reflection type liquid crystal display device having four sets of 13.3 inch panels.

[Example 3] (Production of λ / 4 plate for display surface side) The roll film λ / 4 plate QF-2 produced in Example 2 was prepared by using the method described in JP-A-7-2947.
An RGB color filter was formed by the photographic method described in JP-A-14. A gas barrier layer and a transparent electrode were formed on the λ / 4 plate having this color filter by the same method as in Example 1 to obtain a λ / 4 plate having a color filter, a gas barrier layer and a transparent electrode. Zigzag mountain-shaped protrusions were formed on the transparent electrode of the λ / 4 plate by a photoresist in order to control the orientation. The ridgeline of this projection forms 45 ° with respect to the longitudinal direction of the roll film-shaped λ / 4 plate. A vertical alignment film (SE-1211, manufactured by Nissan Chemical Industries, Ltd.) is continuously applied and heat-treated on a roll film plastic substrate on which a color filter layer, a gas barrier layer, a transparent electrode layer, and projections for alignment control are formed. Then, a λ / 4 plate on which a color filter layer, a gas barrier layer, a transparent electrode layer, alignment control protrusions, and an alignment film were formed was produced.

A polyvinyl alcohol adhesive was applied to both sides of the linear polarizing film POL-2 having a transmission axis perpendicular to the longitudinal direction prepared in Example 2, and one of the above λ / 4 was applied to one side.
The polycarbonate side of the plate is the roll-to-roll side of the cellulose triacetate film (protective film) having the antireflection layer / antiglare layer provided on the opposite side in the same manner as in Example 1 without the antireflection layer / antiglare layer. Pasted together
Further dried at 80 ° C., it has a function as a circularly polarizing plate having a width of 680 mm, and has a color filter, a gas barrier layer, a transparent electrode, an alignment control protrusion, an alignment film, and an antireflection layer / antiglare layer. 0.2 mm display surface side plastic substrate S
UB-3U was obtained. Since the effective width of this plastic substrate is 650 mm, the maximum is 42 "(aspect ratio = 4: 3).
We can handle up to panel size.

(Production of λ / 4 Plate for Opposite Side) The roll film type λ / 4 plate QF-2 produced in Example 2 was set in a winding type sputtering device, and was transparent on the display side plastic substrate. An SiOx gas barrier layer having a thickness of 10 nm was formed on the surface opposite to the surface on which the electrode layers and the like were formed. Further, four sets of 13.3 inch TFT arrays made of polysilicon were formed thereon. Further, an Al reflective electrode having an opening with an aperture ratio of 20% was formed on the TFT array, and a 150 nm In ₂ O ₃ based transparent electrode was further formed on the Al reflective electrode. On the transparent electrode of the λ / 4 plate, a mountain-shaped protrusion was formed with a photoresist.
The ridgeline of this projection forms 45 ° with respect to the longitudinal direction of the roll film-shaped λ / 4 plate. Gas barrier layer, TFT,
A vertical alignment film (S) is formed on a roll film-shaped plastic substrate on which a reflective electrode having openings and projections for alignment control are formed.
E-1211, manufactured by Nissan Chemical Industries, Ltd. is continuously applied and heat-treated to produce a λ / 4 plate on which a gas barrier layer, a TFT, a reflective electrode having an opening, an alignment control protrusion, and an alignment film are formed. did.

Polyvinyl alcohol adhesive was applied to both sides of the above-mentioned linearly polarizing film POL-2 having a transmission axis perpendicular to the longitudinal direction prepared in Example 2, and the above-mentioned λ / 4 was applied to one side.
The polycarbonate side of the plate is opposite to the opposite side of the cellulose triacetate film (protective film) to which an antireflection layer / antiglare layer has been applied in advance as in Example 2, and the side without the antireflection layer / antiglare layer is roll-to-roll. Pasted together
Further dried at 80 ° C., it has a function as a circularly polarizing plate having a width of 680 mm, and has a color filter, a gas barrier layer, a transparent electrode, an alignment control protrusion, an alignment film, and an antireflection layer / antiglare layer. A 0.2 mm display surface side plastic substrate SUB-3U was obtained. Since the effective width of this plastic substrate is 650 mm, the maximum is 42 "(aspect ratio = 4:
We can handle panel sizes up to 3).

(Production of Semi-Transmissive Liquid Crystal Display Device) Display surface side plastic substrate SUB-3U produced as described above.
And the opposite side plastic substrate SUB-3L was cut into a size of 550 mm × 650 mm. Two plastic substrates SUB-3U and SUB-3L are stacked with a spacer having a particle diameter of 4 μm so that the alignment films face each other, and a liquid crystal having a negative dielectric anisotropy (MLC-6608, (Manufactured by Merck & Co., Inc.) was injected to form a liquid crystal layer. In this way, a 550 mm × 650 mm VA type liquid crystal cell was produced. The obtained liquid crystal cell was cut to obtain a reflection type liquid crystal display device having four sets of 13.3 inch panels.

(Comparative Example 1) A glass substrate of 550 mm x 650 mm on the opposite side, on which four sets of one TFT array consisting of a reflective electrode and driving polysilicon of 13.3 inches was formed, was prepared. A vertical alignment film (SE-1211, manufactured by Nissan Chemical Industries, Ltd.) is applied to the electrode side of this glass substrate, and heat-treated at 80 ° C. for 15 minutes and further at 180 ° C. for 60 minutes to obtain the glass substrate in the short side direction. Was rubbed. The color filter layer, the gas barrier layer, the transparent electrode layer, and the roll film-shaped λ / 4 plate having the alignment film formed in Example 1 were cut into 550 mm × 650 mm sheets,
A rubbing treatment was performed parallel to the side of 550 mm. Particle size 4
The λ / 4 plate that had been subjected to the above rubbing treatment was placed on the opposite side substrate with the alignment films facing each other through a spacer of μm. At this time, the rubbing directions of the upper and lower substrates facing each other were anti-parallel. A liquid crystal having a negative dielectric anisotropy (MLC-6608, manufactured by Merck Ltd.) was injected into the gap between the substrates to form a liquid crystal layer. In this way, 550 mm x 650 mm
A VA type liquid crystal cell was manufactured. The obtained liquid crystal cell was cut and divided into four sets of 13.3 inch panels. Furthermore, it is a commercially available polarizing plate (HLC2-5618AGK, manufactured by Sanritz Co., Ltd.) having a transmission axis in the width direction in the roll form, and a sheet having a width of 650 mm, the side after cutting forms 45 ° with the longitudinal direction of the roll form. Thus, a 13.3-inch size polarizing plate was cut out. 13. This polarizing plate was manufactured.
It was attached to the display surface side of the 3-inch panel via an adhesive material. To prepare a circularly polarizing plate from a λ / 4 plate having a width of 650 mm and a slow axis in the longitudinal direction of the roll and a polarizing plate having a width of 650 mm and a transmission axis in the width direction of the roll,
Only the panel size of maximum size 36.5 "(aspect ratio = 4: 3) can be supported. The thickness of the plastic substrate on the display side where the λ / 4 plate and the polarizing plate are attached is 0.33 mm.
Met.

[0082]

EFFECTS OF THE INVENTION According to the present invention, (1) there is little loss during punching, the yield is high, (2) large size can be accommodated, and (3)
Since the λ / 4 plate and the linear polarization film are punched together, the punching process can be reduced, and (4) the λ / 4 plate and the linear polarization film are attached by roll-to-roll, so that each chip is attached. There is no need to adjust the angle, and (5) the deviation of the bonding angle is small. (6) A thin circularly polarizing plate was obtained. That is, a linear polarizing film having a transmission axis inclined by 45 ° with respect to the longitudinal direction or λ having a slow axis inclined by 45 ° with respect to the longitudinal direction.
When a circularly polarizing plate was manufactured using a / 4 plate, the productivity was significantly improved. As a result, it is possible to obtain a liquid crystal display device which is lightweight and has flexibility so that the substrate is not easily damaged, and a plastic substrate for the same, particularly in a reflective liquid crystal display device used for carrying.

[Brief description of drawings]

FIG. 1 is a schematic view showing a tenter stretching machine for a linear polarizing plate.

2 is a cross-sectional view of the liquid crystal cell of Example 1. FIG.

FIG. 3 is a sectional view of a liquid crystal cell of Example 2.

FIG. 4 is a cross-sectional view of a liquid crystal cell of Example 3.

FIG. 5 is a sectional view of a liquid crystal cell of Example 4.

[Explanation of symbols]

1 Antireflection Layer / Antiglare Layer 2 Protective Film 3 Linear Polarizing Film 4 λ / 4 Plate 5 Color Filter 6 Gas Barrier Film 7 Transparent Conductive Film 8 Alignment Film 9 Liquid Crystal Layer 10 Reflective Electrode 11 TFT 12 Glass Substrate 13 Semitransparent Film 14 Opening Reflective electrode 15 having parts Adhesive layer (a) Film introduction direction (b) Film transport direction to the next step (a) Film introduction step (b) Film stretching step (c) Stretched film is sent to the next step Step A1 Bite position of the film into the holding means and the starting point stone for film extension (substantially holding start point: right) B1 film staying position in the holding means (left) C1 Film starting point position (substantially holding start point: Left) Cx film release position and film stretching end point reference position (substantially holding release point: left) Ay film stretching end point reference position (substantially holding release point:
Right) | L1-L2 | Stroke difference between left and right film holding means W Substantial width θ at the end of the stretching process of the film θ Angle between the stretching direction and the film advancing direction 21 Center line of the introduction side film 22 Center of the film sent to the next process Line 23 Trajectory of film holding means (left) 24 Trajectory of film holding means (right) 25 Introducing film 26 Films 27, 27 'sent to the next process Left and right film holding start (engagement) points 28, 28' Left and right Departure point from the film holding means

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02F 1/13363 G02F 1/13363 F term (reference) 2H049 BA02 BA03 BA07 BA25 BA42 BB43 BB44 BB63 BB66 BC03 BC22 2H090 JA06 JB03 JB10 JC01 LA07 LA08 LA09 LA20 MA01 2H091 FA08X FA08Z FA11X FA14Z FB02 FD05 FD08 GA06 LA12 4F100 AK01A AT00A BA02 GB41 JN10A JN10B

Claims (11)

[Claims] 1. λ / comprising a roll-shaped polymer film
A roll-shaped circularly polarizing plate in which four plates and a roll-shaped linear polarization film are laminated. 2. The angle between the longitudinal direction of the rolled circularly polarizing plate and the slow axis of the λ / 4 plate is substantially 45 °, and the widthwise direction of the rolled circularly polarizing plate and the transmission axis of the linear polarizing film. 2. The rolled circularly polarizing plate according to claim 1, wherein are substantially parallel to each other. 3. The angle between the longitudinal direction of the roll-shaped circularly polarizing plate and the transmission axis of the linear polarizing film is substantially 45 °, and the longitudinal direction of the rolled circularly polarizing plate and the slow axis of the λ / 4 plate. 2. The rolled circularly polarizing plate according to claim 1, wherein are substantially parallel to each other. 4. A λ / comprising a roll-shaped polymer film
4 plates have retardation values measured at a wavelength of 450 nm in the range of 60 to 135 nm, and 100 to 170
The roll shape according to claim 1, which has a retardation value measured at a wavelength of 590 nm in a range of nm and a value obtained by subtracting the retardation value measured at a wavelength of 450 nm from the retardation value measured at a wavelength of 590 nm is 2 nm or more. Circular polarizing plate. 5. A λ / comprising a roll-shaped polymer film
A roll-shaped liquid crystal cell substrate in which four plates and a roll-shaped linear polarization film are laminated, and an angle between the longitudinal direction of the roll-shaped liquid crystal cell substrate and the slow axis of the λ / 4 plate is substantially 45 °. And the width direction of the roll-shaped liquid crystal cell substrate and the transmission axis of the linear polarizing film are substantially parallel to each other. 6. A λ / comprising a roll-shaped polymer film
A roll-shaped liquid crystal cell substrate in which four plates and a roll-shaped linear polarization film are laminated, wherein the angle between the longitudinal direction of the liquid crystal cell substrate and the transmission axis of the linear polarization film is substantially 45 °, and the roll A roll-shaped liquid crystal cell substrate in which the longitudinal direction of the liquid crystal cell substrate and the slow axis of the λ / 4 plate are substantially parallel to each other. 7. A liquid crystal display device comprising a liquid crystal sandwiched between two substrates, wherein the substrate on the side opposite to the display surface has a reflecting means, and the substrate on the display surface side is defined by claim 5 or A reflective liquid crystal display device, which is a substrate obtained by cutting the roll-shaped liquid crystal cell substrate according to item 6. 8. A liquid crystal display device comprising a liquid crystal sandwiched between two substrates, wherein the substrate on the side opposite to the display surface has a semi-transmissive means, and the substrate on the display surface side is defined by claim 5. Alternatively, a semi-transmissive liquid crystal display device is a substrate obtained by cutting the roll-shaped liquid crystal cell substrate described in 6. 9. A liquid crystal display device comprising a liquid crystal sandwiched between two substrates, wherein the substrate on the side opposite to the display surface is obtained by cutting the rolled liquid crystal cell substrate according to claim 5. A transflective liquid crystal display device, characterized in that it is a substrate. 10. The substrate on the display surface side is also the substrate according to claim 5 or 6.
The transflective liquid crystal display device according to claim 9, which is a substrate obtained by cutting the roll-shaped liquid crystal cell substrate according to claim 10. 11. The liquid crystal display device according to claim 7, wherein the liquid crystal molecules are substantially vertically aligned with no voltage applied.